Low emission adsorbent and canister system

ABSTRACT

The present description provides low DBL bleed emission performance properties that allows the design of evaporative fuel emission control systems that are simpler and more compact than those possible by prior art by inclusion of a vent-side volume comprising a parallel passage adsorbent such as a carbon honeycomb with narrow channel width and low cell pitch.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a Continuation of U.S. patent applicationSer. No. 17/216,36, filed 29 Mar. 2021, titled: Low Emission Adsorbentand Canister System, which claims the benefit of priority under 35U.S.C. 119(e) to U.S. Provisional Patent Application 63/001,164, titled:Low Emission Adsorbent and Canister System, filed: 27 Mar. 2020, andU.S. Provisional Patent Application 63/111,768, titled: Low EmissionAdsorbent and Canister System, filed: 10 Nov. 2020, all of which areincorporated herein by reference in their entirety.

BACKGROUND

1. Field of the Discovery. The present disclosure, in variousembodiments, relates generally to evaporative emission control systems.

2. Background Information. Evaporation of gasoline fuel from motorvehicle fuel systems is a major potential source of hydrocarbon airpollution. These fuel vapor emissions occur when the vehicle is running,refueling, or parked (i.e., engine off). Such emissions can becontrolled by the canister systems that employ activated carbon toadsorb the fuel vapor emitted from the fuel systems. Under certain modesof engine operation, the adsorbed fuel vapor is periodically removedfrom the activated carbon by purging the canister systems with ambientair to desorb the fuel vapor from the activated carbon. The regeneratedcarbon is then ready to adsorb additional fuel vapor.

It is well known in the art that a more space efficient activated carbonadsorbent for this concentration-swing application is characterized byan n-butane vapor adsorption isotherm that has adsorption capacitysteeply sloped towards high vapor partial pressures (U.S. Pat. No.6,540,815). In that way, the adsorbent has a high capacity at relativelyhigh concentrations of the type of vapors present with gasoline fuel,and the adsorbent favors release of these captured vapors when exposedto a low vapor concentration or partial pressure, such as during purge.These high performance activated carbons have a large amount of porevolume as “small mesopores” (e.g., SAE Technical Papers 902119 and2001-03-0733, and Burchell 1999, pp. 252-253), which are preferablyabout 1.8 nm to about 5 nm in size as measured by the Barrett, Joynerand Halenda (BJH) method of analysis of nitrogen adsorption isotherms(e.g., U.S. Pat. No. 5,204,310). (According to IUPAC classification,small mesopores are pores of about 1.8-2 nm size within the <2 nmmicropore size range, plus pores of about 2-5 nm size within the 2-50 nmmesopore size range). The small mesopores are sufficiently small tocapture vapors as a condensed phase, and yet readily empty upon exposureto a low partial pressure of vapor. Accordingly, the volume in thesepores correlates linearly with the recoverable vapor capacity by theadsorbent in a canister volume, known as gasoline working capacity(GWC), and likewise correlates linearly with the ASTM butane workingcapacity (herein, “ASTM BWC”) of the adsorbent, as measured by thestandard ASTM 5228 method, which are incorporated herein by reference.The range of ASTM BWC of commercial activated carbon products for thisapplication is from about 3 to about 17 g/dL, with 9+g/dL BWC carbonsfavored for working capacity towards the fuel vapor source of thecanister system, and lower BWC carbons used in one or more subsequentvolumes towards the atmosphere port or vent-side (i.e., vent-sideadsorbent volumes). Generally, cylindrical pellet and other engineeredshaped (e.g., spherical granule) activated carbons are preferred overirregularly shaped or crushed particulates, especially for canistersystems where moderated flow restriction is required such as for vaporcapture during refueling. Advantages of pelletized and engineered shapedactivated carbons include good mechanical strength, low dust, lowdusting rate, high on-size yield in processing, and a narrow particlesize distribution that provides consistency across liter-size canisterfills after bulk shipment and handling.

Though a highly mesoporous adsorbent is favored for working capacity,high ASTM BWC of the adsorbent and its high GWC appear to run counter,in practice, from the concurrent need of the fuel vapor emission controlsystem to provide low emissions even when the vehicle is not operating.

For example, an increase in environmental concerns has continued todrive strict regulations of hydrocarbon emissions. When a vehicle isparked in a warm environment during the daytime (i.e., diurnal heating),the temperature in the fuel tank increases resulting in an increasedvapor pressure in the fuel tank. Normally, to prevent the leaking of thefuel vapor from the vehicle into the atmosphere, the fuel tank is ventedthrough a conduit to a canister containing suitable fuel adsorbentmaterials that can temporarily adsorb the fuel vapor. The canisterdefines a vapor or fluid stream path such that when the vehicle is atrest the fuel vapor of fluid passes from the fuel tank, through the fueltank conduit, through one or more adsorbent volumes, and out to a ventport, which opens to the atmosphere. A mixture of fuel vapor and airfrom the fuel tank enters the canister through a fuel vapor inlet of thecanister and diffuses into the adsorbent volume where the fuel vapor isadsorbed in temporary storage and the purified air is released to theatmosphere through a vent port of the canister. Once the engine isturned on, ambient air is drawn into the canister system through thevent port of the canister. The purge air flows through the adsorbentvolume inside the canister and desorbs the fuel vapor adsorbed on theadsorbent volume before entering the internal combustion engine througha fuel vapor purge conduit. The purge air does not desorb the entirefuel vapor adsorbed on the adsorbent volume, resulting in a residuehydrocarbon (“heel”) that may be emitted to the atmosphere.

In addition, the heel in local equilibrium with the gas phase alsopermits fuel vapors from the fuel tank to migrate through the canistersystem as emissions. Such emissions typically occur when a vehicle hasbeen parked and subjected to diurnal temperature changes over a periodof several days, commonly called “diurnal breathing loss” (DBL)emissions. The California Low Emission Vehicle Regulations made itdesirable for these DBL emissions from the canister system to be below10 mg (“PZEV”) for a number of vehicles beginning with the 2003 modelyear and below 50 mg, typically below 20 mg, (“LEV-II”) for a largernumber of vehicles beginning with the 2004 model year.

Now the California Low Emission Vehicle Regulation (“LEV-III”) andUnited States Federal Tier 3 regulations require canister DBL emissionsnot to exceed 20 mg as per the Bleed Emissions Test Procedure (BETP) aswritten in the California Evaporative Emissions Standards and TestProcedures for 2001 and Subsequent Model Motor Vehicles, Mar. 22, 2012.Furthermore, the regulations on DBL emissions continue to createchallenges for the evaporative emission control systems, especially whenthe level of purge air is low. For example, the potential for DBLemissions may be more severe for a hybrid vehicle, including a vehiclewhose powertrain is both an internal combustion engine and an electricmotor (“HEV”), and a vehicle where there is a start-stop system thatautomatically shuts down and restarts the internal combustion engine toreduce the amount of time the engine spends idling, thereby reducingfuel consumption and tailpipe emissions. In such hybrid vehicles, theinternal combustion engine can be turned off nearly half of the timeduring vehicle operation. Since the adsorbed fuel vapor on theadsorbents is purged only when the internal combustion engine is on, theadsorbents in the canister of a hybrid vehicle are purged with fresh airless than half of the time compared to conventional vehicles andfrequently within the range of 55 bed volumes (BV) to 100 BV (based onU.S. EPA Federal Test Procedure (FTP)-75 drive cycle), where “By” is theratio of the total volume of purge flow relative to the volumes ofadsorbent in the canister system. And yet, hybrid vehicles generatenearly the same amount of evaporative fuel vapor as conventionalvehicles. The lower purge frequency and lower purge volume of the hybridvehicle can be insufficient to clean the residue hydrocarbon heel fromthe adsorbents in the canister, resulting in high DBL emissions. Otherpowertrains when engineered for optimum drive performance, fuelefficiency and tailpipe emissions, are similarly challenged to provide ahigh level of purge for refreshing the canister and are challenged toprovide optimum air-fuel mixtures and rates to the engine. Thesepowertrains include turbocharged or turbo-assisted engines, and gasolinedirect injection (“GDI”) engines.

Globally, by contrast, evaporative emission regulations have been lessstringent than in the US, but the trend is now for more stringentregulations, along the path that the US has taken. There is increasedrecognition of the benefits from tighter controls for better use ofvehicle fuel and for cleaner air, especially in regions where light dutyvehicle use is growing rapidly and air quality issues require urgentattention. As a notable example, the Ministry of EnvironmentalProtection of the People's Republic of China released regulations in2016 that include limitations on fuel vapor emissions, forimplementation in 2020 (See “Limits and Measurement Methods forEmissions from Light-Duty Vehicles, GB 18352.6-2016, also known as“China 6”). This standard specifies the limits and measurement methodsfor light-duty vehicles, including hybrid electric vehicles, equippedwith positive ignition engines for exhaust emissions in regular and lowtemperatures, real driving emissions (RDE), crankcase emissions,evaporative emissions and refueling emissions, technical requirements,and measurement methods of the durability for pollution controlequipment, and onboard diagnostic system (OBD).

While the testing protocol and the emissions limits for the wholevehicle testing are provided in the regulations, there is leeway in theallocation by the vehicle manufacturers for the design limits of thecomponents contributing to the total emissions (e.g., evaporativeemission control canister system, fuel tank walls, hoses, tubing, etc.).Among the allocations, the limit for the evaporative emission controlcanister system is generally set in the fuel system and vehicle designprocesses to be less than 100 mg for the worst day DBL emissions as partof the design balance for meeting the overall vehicle requirements ofChina 6 regulations.

In order to meet the evaporative fuel emission regulatory standards inthe vehicle design stage, vehicle manufacturers typically providepotential suppliers with target specifications on overall canistersystem performance, in terms of functional content, appearance, physicalcharacteristics, and durability, hence leaving appropriate designflexibility for achieving those targets to the canister systemmanufacturers. For example, General Motors Corporation sets many designspecifications for evaporative emission control canister systems (SeeGMW16494). A notable specification is the total allowable pressure dropof a carbon canister system. In this example, the maximum flowrestriction for a canister system intended for on-board refueling vaporrecovery (ORVR) “shall be 0.90±0.225 kPa at 60 liter/min (lpm) air flow. . . as measured at the tank tube while flowing air from the canistertank tube to the fresh air tube” (see Section 3.2.1.3.2.2 of GMW-16494).This specification and others in GMW-16494 offer examples of the degreethat vehicle manufacturer allow for flow restriction.

As a result of such specifications, canister system designers appreciatea wide array of chamber design and adsorbent selection options because,in addition to varied fuel emissions regulations around the world, thedemands are quite varied across different vehicle platforms fromdifferent vehicle manufacturers per engine type, engine operationaldesign, space availability, purge availability, and canister systemcontrol strategy. Certainly, “one size does not fit all” for canistersystem design and its adsorbent fills.

For satisfying the apparently opposing needs of high working capacityand low DBL emission performance, several approaches have been reported.One approach is to significantly increase the volume of purge gas toenhance desorption of the residue hydrocarbon heel from the adsorbentvolume. See U.S. Pat. No. 4,894,072. This approach, however, has thedrawback of complicating management of the fuel/air mixture to theengine during the purge step and tends to adversely affect tailpipeemissions, and such high levels of purge are simply unavailable forcertain powertrain designs. At the cost of design and installation, anauxiliary pump may be employed at some location within the evaporativeemission control system to supplement, assist, or augment the purge flowor volume, as a means to complement the engine vacuum and to avoid someissues with engine performance and tailpipe emission control whenotherwise depending on the engine vacuum alone.

Another approach is to design the canister to have a relatively lowcross-sectional area on the vent-side of the canister, either by theredesign of existing canister dimensions or by the installation of asupplemental vent-side canister of appropriate dimensions. This approachreduces the residual hydrocarbon heel by increasing the intensity ofpurge air. One drawback of such approach is that the relatively lowcross-sectional area imparts an excessive flow restriction to thecanister system. See U.S. Pat. No. 5,957,114.

Another approach for increasing the purge efficiency is to heat thepurge air, or a portion of the adsorbent volume having adsorbed fuelvapor, or both. However, this approach increases the complexity ofcontrol system management and poses some safety concerns. See U.S. Pat.Nos. 6,098,601 and 6,279,548.

Another approach is to route the fuel vapor through a fuel-sideadsorbent volume, which is located proximal to the fuel source in thefluid stream, and then at least one subsequent (i.e., vent-side)adsorbent volume, which is located down-stream from the fuel-sideadsorbent, prior to venting to the atmosphere, wherein the fuel-sideadsorbent volume (herein, the initial adsorbent volume”) has a higherisotherm slope, defined as an incremental adsorption capacity, than thesubsequent (i.e., vent-side) adsorbent volume. See U.S. Pat. No.RE38,844, which is incorporated herein by reference in its entirety.

Another approach, especially useful when only a low level of purge mightbe available, is to route the fuel vapor through at least one subsequent(i.e., vent-side) adsorbent comprising a window of incrementaladsorption capacity, volume-averaged ASTM BWC, a particular g-total BWCcapacity, and/or substantially uniform structure that facilitatesapproximately uniform air and vapor flow distribution across its flowpath cross section. See U.S. Pat. Nos. 9,732,649 and 10,960,342, whichare both incorporated herein by reference in their entirety.

One effective format for a subsequent adsorbent volume with lowincremental adsorption capacity towards the vent-side of the canistersystem is an elongated, cylindrically shaped, ceramic-bound activatedcarbon honeycomb, such as Nuchar® HCA or HCA-LBE (Ingevity®, NorthCharleston, S.C., USA), typically available in diameters of 29, 35 and41 mm and certain lengths between 50 and 200 mm. The internal parallelpassage structure is a square grid of about 200 cells per square inch(cpsi), with cell walls of about 0.3 mm in thickness. These engineeredparts are costly to make, requiring special skill and equipment tomanufacture. Care must be taken for precise control of ingredientproperties, formulation, mixing, extrusion, thermal processing, andcutting in order to meet final product specifications of mechanicalstrength, adsorptive capacity, and flow restriction. The finishedadsorbent part must be durable, defect-free and dimensionally exact, andit must perform for emissions control over virtually the life of thevehicle. Though quite effective as a vent-side adsorbent volume fill forcontrolling diurnal breathing loss emissions, these ceramic-boundhoneycombs, for some fuel systems, require larger size parts andmultiple parts in-series for meeting emission control targets. Evenstill, under extremely low purge levels, the honeycombs may not be ableto meet emission control targets, resulting in the use of very costlysealed tank fuel systems.

Accordingly, new adsorbent options and approaches for balancing thetradeoffs in terms of cost, size, flow restriction, working capacity,diurnal breathing loss (DBL) performance, complexity, and placementflexibility, are in high demand. For example, it would be desirable tohave a higher performing adsorbent honeycomb that could allow smallerand less complicated approaches for system design and operation, bothfor when normal levels or low levels of purge are available.

SUMMARY

Presently described is an adsorbent material in the form of a parallelpassage adsorbent volume (PPAV) that is configured to providesurprisingly and unexpectedly low DBL bleed emission performanceproperties when incorporated into a vehicle emissions canister system,evaporative emission control canister systems, and methods of using thesame. The described PPAV advantageously allows the design of evaporativefuel emission control systems that are simpler and more compact thanthose currently known or available. As described herein, when testedunder a standard vapor cycling protocol, an evaporative emission controlcanister system comprising a PPAV as described herein demonstratedsignificantly lower emissions using a standard bleed emission testprocedure, for example, the BETP as written in the CaliforniaEvaporative Emissions Standards and Test Procedures for 2001 andSubsequent Model Motor Vehicles, Mar. 22, 2012.

Thus, in one aspect, the description provides a PPAV comprising an outersurface and a plurality of parallel passages or channels extendingtherethrough parallel to the outer surface, and wherein the parallelpassages or channels are configured to have at least one of an averagechannel hydraulic diameter (herein, “t_(c,Dh)”) of less than 1.25 mm, ahydraulic diameter cell pitch (herein, “CP_(Dh)”) of less than 1.5 mm,or a combination thereof. As detailed herein, when incorporated intoevaporative emission systems, PPAVs as described herein surprisingly andunexpectedly resulted in reduced DBL bleed emissions while providing forless complicated design.

In another aspect, the description provides an evaporative emissioncontrol canister system comprising one or more canisters including afuel-side adsorbent volume, and at least one vent-side parallel passageadsorbent volume (PPAV), wherein the at least one vent-side PPAVcomprises an outer surface and a plurality of parallel passages orchannels extending therethrough parallel to the outer surface, andwherein the parallel passages or channels are configured to have atleast one of an average channel hydraulic diameter (t_(c,Dh)) of lessthan or equal to 1.25 mm, a hydraulic diameter cell pitch (CP_(Dh)) ofless than or equal to 1.5 mm, or a combination thereof. In other aspectsor embodiments described herein, the description provides an evaporativeemission control system comprising a fuel tank for storing fuel, anengine having an air induction system and adapted to consume fuel, andone or more canisters including a fuel-side adsorbent volume and atleast one vent-side PPAV, wherein the at least one vent-side PPAVcomprises an outer surface and a plurality of parallel passages orchannels extending therethrough parallel to the outer surface, andwherein the parallel passages or channels are configured to have atleast one of an average channel hydraulic diameter (t_(c,Dh)) of lessthan or equal to 1.25 mm, a hydraulic diameter cell pitch (CP_(Dh)) ofless than or equal to 1.5 mm, or a combination thereof, and

wherein the canister includes a fuel vapor inlet conduit connecting theevaporative emission control canister system to the fuel tank;

a fuel vapor purge outlet conduit connecting the evaporative emissioncontrol canister system to the air induction system of the engine; and

a vent conduit for venting the evaporative emission control canistersystem to the atmosphere and for admission of purge air to theevaporative emission control canister system, wherein the evaporativeemission control canister system is defined by a fuel vapor flow pathfrom the fuel vapor inlet conduit to the fuel-side adsorbent volumetoward the at least one PPAV and the vent conduit, and by an air flowpath from the vent conduit to the at least one PPAV toward the fuel-sideadsorbent volume and the fuel vapor purge outlet.

In any of the aspects or embodiments described herein, the evaporativeemission control canister system has a two-day diurnal breathing loss(DBL) of no more than 50 mg at no more than 315 liters of purge or nomore than 150 bed volumes (BV) applied after a 40 g/hr butane loadingstep as determined by the 2012 California Bleed Emissions Test Procedure(BETP).

In any of the aspects or embodiments described herein, the PPAVcomprises an adsorbent material selected from the group consisting ofactivated carbon, carbon charcoal, zeolites, clays, porous polymers,porous alumina, porous silica, molecular sieves, kaolin, titania, ceria,metal organic framework, and combinations thereof.

In any of the aspects or embodiments described herein, the shaped PPAVadsorbent material comprises activated carbon derived from a materialincluding a member selected from the group consisting of wood, wooddust, wood flour, cotton linters, peat, coal, coconut, lignite,carbohydrates, petroleum pitch, petroleum coke, coal tar pitch, fruitpits, fruit stones, nut shells, nut pits, sawdust, palm, vegetables,synthetic polymer, natural polymer, lignocellulosic material, andcombinations thereof. In any of the aspects or embodiments describedherein, the shaped PPAV adsorbent material comprises activated carbonderived from at least one of wood, wood dust, wood flour, cottonlinters, peat, coal, coconut, lignite, carbohydrates, petroleum pitch,petroleum coke, coal tar pitch, fruit pits, fruit stones, nut shells,nut pits, sawdust, palm, vegetables or a combination thereof.

In any of the embodiments described herein, the evaporative emissioncontrol system may further comprise a heating unit.

In an additional aspect, the description provides methods for reducingfuel vapor emissions in an evaporative emission control system, themethod comprising contacting the fuel vapor with an evaporative emissioncontrol system as described herein, comprising a PPAV as describedherein.

The preceding general areas of utility are given by way of example onlyand are not intended to be limiting on the scope of the presentdisclosure and appended claims. Additional objects and advantagesassociated with the compositions, methods, and processes of the presentinvention will be appreciated by one of ordinary skill in the art inlight of the instant claims, description, and examples. For example, thevarious aspects and embodiments of the invention may be utilized innumerous combinations, all of which are expressly contemplated by thepresent description. These additional advantages objects and embodimentsare expressly included within the scope of the present invention. Thepublications and other materials used herein to illuminate thebackground of the invention, and in particular cases, to provideadditional details respecting the practice, are incorporated byreference.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are incorporated into and form a partof the specification, illustrate several embodiments of the presentinvention and, together with the description, serve to explain theprinciples of the invention. The drawings are only for the purpose ofillustrating an embodiment of the invention and are not to be construedas limiting the invention. Further objects, features and advantages ofthe invention will become apparent from the following detaileddescription taken in conjunction with the accompanying figures showingillustrative embodiments of the invention, in which:

FIG. 1 is a cross-sectional view of an exemplary evaporative emissioncontrol canister system (100) as described herein.

FIG. 2 . is a cross-sectional view of an exemplary evaporative emissioncontrol canister system (100) as described herein.

FIG. 3 is a cross-sectional view of an exemplary evaporative emissioncontrol canister system (100) as described herein, including fouradsorbent volumes in the main canister (201, 202, 203, and 204), and anauxiliary canister (300) including a subsequent adsorbent volume (301)therein.

FIG. 4 is a cross-sectional view of an exemplary evaporative emissioncontrol canister system (100) as described herein, including fouradsorbent volumes in the main canister (201, 202, 203, and 204), and anauxiliary canister (300) including two subsequent adsorbent volumes(301, 302) therein.

FIG. 5 is a cross-sectional view of an exemplary evaporative emissioncontrol canister system (100) illustrating a system with which the DBLemissions performance of the comparative and inventive examples aremeasured, including three adsorbent volumes in the main canister (501,203, 204) when a single PPAV honeycomb (502) is present in an auxiliaryvent-side canister (300).

FIG. 6 is a cross-sectional view of an exemplary evaporative emissioncontrol canister system (100) illustrating a system with which the DBLemissions performance of the comparative and inventive examples aremeasured when there are only two adsorbent volumes in the main canister(501, 202) and there is one PPAV honeycomb (502) present in an auxiliaryvent-side canister (300).

FIG. 7 is a cross-sectional view of an exemplary evaporative emissioncontrol canister system (100) illustrating a system with which the DBLemissions performance of the comparative and inventive examples aremeasured when there are only two adsorbent volumes in the main canister(501, 202) and there are two PPAV honeycombs (502, 504) present insidein-series auxiliary vent-side canisters (300, 503).

FIG. 8 is a cross-sectional view of an exemplary evaporative emissioncontrol canister system (100) illustrating a system with which DBLemissions performance of the comparative and inventive examples aremeasured when there are three adsorbent volumes in a portion of the maincanister (501, 203, 204), and two PPAV honeycombs (502, 504) presentin-series in another portion of the canister.

FIG. 9 is a diagram that illustrates the cross-sectional features of ahoneycomb-based PPAV as described herein and illustrates the cell wallthickness (t_(w)), channel width (t_(c)), channel area (A_(c)), channelperiphery length (P_(c)), and skin thickness (t_(a)) for an exemplaryhoneycomb-shaped PPAV as described herein.

FIG. 10 is a diagram that illustrates the four rotations from which theouter diameters (D_(o)) of the exemplary honeycomb-shaped PPAVs weremeasured in both caliper and image analysis measurements.

FIG. 11 is a diagram that illustrates the four rotations from which theinner diameters (D_(i)) of the exemplary honeycomb-shaped PPAVs weremeasured in image analysis measurements.

FIG. 12 is a diagram that illustrates the vertical and horizontalcrosshairs from which mid-channel widths and wall thickness (t_(c,m) andt_(w,m)) and base-channel widths and wall thickness (t_(c,b) andt_(w,b)) were obtained via image analysis of exemplary honeycomb-shapedPPAVs.

FIG. 13 is a diagram that illustrates the n-by-n (“n×n”) square cellgrid from which the n×n grid channel width (t_(c,n×n)) and n×n wallthickness (t_(c,m) and t_(w,n×n)) were obtained via image analysis ofexemplary honeycomb-shaped PPAVs.

FIG. 14 is an illustration of effluent concentration response featuresfor a virgin PPAV during the initial saturation according to the dynamicbutane adsorption capacity test. Efficiency is the cumulative massfraction adsorbed (shaded area) relative to the cumulative influent massup to a point of saturation (e.g., 95%).

FIG. 15 is an illustration of effluent concentration response featuresfor a cycled PPAV, during the saturation step after the initialsaturation and purge steps, according to the dynamic butane adsorptioncapacity test. For a PPAV cycled through prior adsorption and purge,there is likewise an MTZ breakthrough. Additionally, a residual heelfrom the incomplete adsorbate removal from the prior purge step resultsin a bleed through of adsorbate in the effluent prior to thebreakthrough of the MTZ.

FIG. 16 is an illustration of effluent concentration response featuresfor a cycled PPAV, during the saturation step after the initialsaturation and purge steps, according to the dynamic butane adsorptioncapacity test, for an intermediate breakthrough point of 25% of the 0.5vol % influent butane concentration.

FIG. 17 is test data for 35 mm diameter×150 mm long comparative (opencircles) and inventive examples (filled circles) for day 2 DBL emissionsas a function of PPAV average channel hydraulic diameter (t_(c,Dh)).

FIG. 18 are test data for 35 mm diameter×150 mm long comparative (opencircles) and inventive examples (filled circles) for day 2 DBL emissionsas a function of PPAV channel hydraulic diameter cell pitch (CP_(Dh)).

FIG. 19 are test data for 35 mm diameter×150 mm long comparative (opencircles) and inventive examples (filled circles) for day 2 DBL emissionsas a function of PPAV channel width plurality (t_(c,avg)).

FIG. 20 are test data for 35 mm diameter×150 mm long comparative (opencircles) and inventive examples (filled circles) for day 2 DBL emissionsas a function of PPAV cell pitch based on channel width plurality(CP_(tc,avg); i.e., “plurality width cell pitch”).

FIG. 21 are test data for 35 mm diameter×150 mm long comparative (opencircles) and inventive examples (filled circles) for day 2 DBL emissionsas a function of PPAV cell density (cells per square inch; cpsi).

FIG. 22 are test data for 35 mm diameter×150 mm long comparative (opencircles) and inventive examples (filled circles) for day 2 DBL emissionsas a function of PPAV cell wall thickness (t_(w,avg)).

FIG. 23 are test data for 35 mm diameter×150 mm long comparative (opencircles and open squares) and inventive examples (filled circles andfilled squares) for macropore ratios (M/M and M/m) as a function of celldensity (cells per square inch; cpsi).

FIG. 24 are test data for 35 mm diameter×150 mm long comparative (opencircles and open squares) and inventive examples (filled circles andfilled squares) for macropore volumes (PV) as a function of cell density(cells per square inch; cpsi).

FIG. 25 are test data for 35 mm diameter×150 mm long comparative (opencircles) and inventive examples (filled circles) for day 2 DBL emissionsas a function of the PPAV flow restriction at 40 lpm (kPa).

FIG. 26 are test data for 35 mm diameter×150 mm long comparative (opencircles) and inventive examples (filled circles) for day 2 DBL emissionsas a function of the PPAV average channel hydraulic diameter(t_(c, Dh)).

FIG. 27 are test data for 29 mm diameter×150 mm long comparative (opendiamond) and inventive examples (filled diamond), and PPAV withslit-shaped cells (filled rectangles) for day 2 DBL emissions as afunction of the PPAV cell density (cells per square inch; cpsi).

FIG. 28 are test data for 29 mm diameter×150 mm long comparative (opendiamond) and inventive examples (filled diamond), and PPAV withslit-shaped cells (filled rectangles) for day 2 DBL emissions as afunction of the PPAV cell pitch based on hydraulic diameter (CP_(Dh)).

FIG. 29 are test data for 29 mm diameter×150 mm long comparative (opendiamond) and inventive examples (filled diamond), and PPAV withslit-shaped cells (filled rectangles) for day 2 DBL emissions as afunction of the PPAV cell pitch based on channel width plurality(CP_(tc, avg)), or based on narrow channel width-based cell pitch forslit-shaped cell examples.

FIG. 30 are test data for comparative (open circles) and inventiveexamples (filled circles) for day 2 DBL emissions as a function of PPAVBWC (g/dL).

FIG. 31 are test data for comparative (open circles) and inventiveexamples (filled circles) for day 2 DBL emissions as a function of PPAVIAC (g/L-bed).

FIG. 32 are test data for comparative (open circles) and inventiveexamples (filled circles) for day 2 DBL emissions as a function ofliters of purge volume (L).

FIG. 33 are test data for comparative (open circles) and inventiveexamples (filled circles) for day 2 DBL emissions as a function of bedvolumes of purge (BV).

FIG. 34 are test data for comparative (open circles) and inventiveexamples (filled circles) for day 2 DBL emissions as a function ofliters of purge volume (L).

FIG. 35 are test data for comparative (open circles) and inventiveexamples (filled circles) for day 2 DBL emissions as a function of bedvolumes of purge (BV).

FIG. 36 are test data for comparative (open circles) and inventiveexamples (filled circles) for virgin part adsorption efficiency(DAE_(V95%)) as a function of cell density (cells per square inch;cpsi).

FIG. 37 are test data for comparative (open circles) and inventiveexamples (filled circles) for virgin part adsorption efficiency(DAE_(V95%)) as a function of cell pitch based on hydraulic diameter(CP_(Dh)).

FIG. 38 are test data for comparative (open circles) and inventiveexamples (filled circles) for cycled part adsorption efficiency(DAE_(C95%)) as a function of cell density (cells per square inch;cpsi).

FIG. 39 are test data for comparative (open circles) and inventiveexamples (filled circles) for cycled part adsorption efficiency(DAE_(C95%)) as a function of cell pitch based on hydraulic diameter(CP_(Dh)).

FIG. 40 are test data for comparative (open circles) and inventiveexamples (filled circles) for cycled part adsorption efficiency(DAE_(C0.125 vol %)) as a function of cell density (cells per squareinch; cpsi).

FIG. 41 are test data for comparative (open circles) and inventiveexamples (filled circles) for cycled part adsorption efficiency(DAE_(C0.125 vol %)) as a function of cell pitch based on hydraulicdiameter (CP_(Dh)).

FIG. 42 are test data for 35 mm diameter×150 mm long comparative (opencircles) and inventive examples (filled circles) for day 2 DBL emissionsas a function of the PPAV mass of bleedthrough (g) before 5% BT.

FIG. 43 are test data for 35 mm diameter×150 mm long comparative (opencircles) and inventive examples (filled circles) for day 2 DBL emissionsas a function of the PPAV percent influent as bleedthrough relative tototal butane delivered before 95% BT.

FIG. 44 are test data for 35 mm diameter×150 mm long comparative (opencircles) and inventive examples (filled circles) for day 2 DBL emissionsas a function of the PPAV bleedthrough relative to total mass adsorbedbefore 95% BT.

FIG. 45 are test data for 35 mm diameter×150 mm long comparative (opencircles) and inventive examples (filled circles) for gasoline workingcapacity (g) as a function of the PPAV cell density (cells per squareinch; cpsi).

FIG. 46 Illustration of the x- and y-axis orientations applied to imageanalysis of PPAV parts with slit-shaped cells.

DETAILED DESCRIPTION

The present disclosure now will be described more fully hereinafter, butnot all embodiments of the disclosure are shown. While the disclosurehas been described with reference to exemplary embodiments, it will beunderstood by those skilled in the art that various changes may be madeand equivalents may be substituted for elements thereof withoutdeparting from the scope of the disclosure. In addition, manymodifications may be made to adapt a particular structure or material tothe teachings of the disclosure without departing from the essentialscope thereof.

Where a range of values is provided, it is understood that eachintervening value between the upper and lower limit of that range andany other stated or intervening value in that stated range isencompassed within the invention. The upper and lower limits of thesesmaller ranges may independently be included in the smaller ranges isalso encompassed within the invention, subject to any specificallyexcluded limit in the stated range. Where the stated range includes oneor both of the limits, ranges excluding either both of those includedlimits are also included in the invention.

The following terms are used to describe the present invention. Ininstances where a term is not specifically defined herein, that term isgiven an art-recognized meaning by those of ordinary skill applying thatterm in context to its use in describing the present invention.

The articles “a” and “an” as used herein and in the appended claims areused herein to refer to one or to more than one (i.e., to at least one)of the grammatical object of the article unless the context clearlyindicates otherwise. By way of example, “an element” means one elementor more than one element.

The phrase “and/or,” as used herein in the specification and in theclaims, should be understood to mean “either or both” of the elements soconjoined, i.e., elements that are conjunctively present in some casesand disjunctively present in other cases. Multiple elements listed with“and/or” should be construed in the same fashion, i.e., “one or more” ofthe elements so conjoined. Other elements may optionally be presentother than the elements specifically identified by the “and/or” clause,whether related or unrelated to those elements specifically identified.Thus, as a non-limiting example, a reference to “A and/or B”, when usedin conjunction with open-ended language such as “comprising” can refer,in one embodiment, to A only (optionally including elements other thanB); in another embodiment, to B only (optionally including elementsother than A); in yet another embodiment, to both A and B (optionallyincluding other elements); etc.

As used herein in the specification and in the claims, “or” should beunderstood to have the same meaning as “and/or” as defined above. Forexample, when separating items in a list, “or” or “and/or” shall beinterpreted as being inclusive, i.e., the inclusion of at least one, butalso including more than one, of a number or list of elements, and,optionally, additional unlisted items. Only terms clearly indicated tothe contrary, such as “only one of” or “exactly one of,” or, when usedin the claims, “consisting of,” will refer to the inclusion of exactlyone element of a number or list of elements. In general, the term “or”as used herein shall only be interpreted as indicating exclusivealternatives (i.e., “one or the other but not both”) when preceded byterms of exclusivity, such as “either,” “one of,” “only one of,” or“exactly one of.”

In the claims, as well as in the specification above, all transitionalphrases such as “comprising,” “including,” “carrying,” “having,”“containing,” “involving,” “holding,” “composed of,” and the like are tobe understood to be open-ended, i.e., to mean including but not limitedto. Only the transitional phrases “consisting of” and “consistingessentially of” shall be closed or semi-closed transitional phrases,respectively, as set forth in the 10 United States Patent Office Manualof Patent Examining Procedures, Section 2111.03.

As used herein in the specification and in the claims, the phrase “atleast one,” in reference to a list of one or more elements, should beunderstood to mean at least one element selected from anyone or more ofthe elements in the list of elements, but not necessarily including atleast one of each and every element specifically listed within the listof elements and not excluding any combinations of elements in the listof elements. This definition also allows that elements may optionally bepresent other than the elements specifically identified within the listof elements to which the phrase “at least one” refers, whether relatedor unrelated to those elements specifically identified. Thus, as anonlimiting example, “at least one of A and B” (or, equivalently, “atleast one of A or B,” or, equivalently “at least one of A and/or B”) canrefer, in one embodiment, to at least one, optionally including morethan one, A, with no B present (and optionally including elements otherthan B); in another embodiment, to at least one, optionally includingmore than one, B, with no A present (and optionally including elementsother than A); in yet another embodiment, to at least one, optionallyincluding more than one, A, and at least one, optionally including morethan one, B (and optionally including other elements); etc. It shouldalso be understood that, unless clearly indicated to the contrary, inany methods claimed herein that include more than one step or act, theorder of the steps or acts of the method is not necessarily limited tothe order in which the steps or acts of the method are recited.

As used herein, the phrase “less than” (e.g., less than about 2) or“less than or equal to” (e.g., less than or equal to about 2) followedby a number, means a non-zero number that is less than the stated numberor a non-zero number that is less than or equal to the stated number,respectively.

As used herein, the terms “fluid,” “gas” or “gaseous” and “vapor” or“vaporous” are used in a general sense and, unless the context indicatesotherwise, are intended to be interchangeable.

Described herein are parallel passage adsorbent volume (PPAV) articles(herein, “shaped PPAV” or “PPAV”) and evaporative emissions controlcanister systems comprising the same that surprisingly and unexpectedlydemonstrate lowered diurnal breathing loss (DBL) emissions as a resultof PPAV being located towards the vent-side of the system. As usedherein, unless the context indicates otherwise, PPAV refers to anindividual article or part (i.e., nominal volume), wherein the PPAVcomprises an adsorbent material and has an outer surface and a pluralityof parallel passages or channels extending therethrough parallel to theouter surface, and wherein the parallel passages or channels areconfigured as described herein.

Thus, in one aspect, the description provides a PPAV comprising an outersurface and a plurality of parallel passages or channels extendingtherethrough parallel to the outer surface, and wherein the parallelpassages or channels are configured to have at least one of an averagechannel hydraulic diameter (t_(c,Dh)) of less than 1.25 mm, a hydraulicdiameter cell pitch (CP_(Dh)) of less than 1.5 mm or a combinationthereof. As detailed herein, when incorporated into evaporative emissionsystems, PPAVs as described herein surprisingly and unexpectedlyresulted in reduced DBL bleed emissions while providing for lesscomplicated design.

In any aspects or embodiments described herein, the average channelhydraulic diameter (t_(c, Dh)) of the PPAV calculated as 4ΣA_(c)/ΣP_(c)as described herein, is independently selected from, for example, lessthan or equal to 1.25 mm, less than or equal to 1.20 mm, less than orequal to 1.10 mm, less than or equal to 1.0 mm; or from about 0.01 mm toabout 1.25 mm, from about 0.1 mm to about 1.25 mm, from about 0.2 mm toabout 1.25 mm, from about 0.3 mm to about 1.25 mm, from about 0.4 mm toabout 1.25 mm; or from about 0.1 mm to about 1.20 mm, from about 0.1 mmto about 1.15 mm, from about 0.1 mm to about 1.10 mm, from about 0.1 mmto about 1.0 mm, from about 0.2 mm to about 1.20 mm, from about 0.2 mmto about 1.15 mm, from about 0.2 mm to about 1.1 mm, from about 0.2 mmto about 1.0 mm, from about 0.3 mm to about 1.25 mm, from about 0.3 mmto about 1.20 mm, from about 0.3 mm to about 1.15 mm, from about 0.3 mmto about 1.1 mm, from about 0.3 mm to about 1.0 mm, from about 0.4 mm toabout 1.25 mm, from about 0.4 mm to about 1.20 mm, from about 0.4 mm toabout 1.15 mm, from about 0.4 mm to about 1.1 mm, from about 0.4 mm toabout 1.0 mm, from about 0.4 mm to about 0.95, or from about 0.4 mm toabout 0.9 mm, and including all subranges and combinations thereof.

In any aspects or embodiments described herein, the hydraulic diametercell pitch (CP_(Dh)) of the PPAV calculated as the sum of averagechannel hydraulic diameter (t_(c, Dh)) plus average wall thickness(t_(w,avg)) as described herein is independently selected from, forexample, less than 1.50 mm, less than 1.40 mm, or less than 1.30 mm; orfrom about 0.5 mm to about 1.5 mm, or from about 0.5 mm to about 1.4 mm,or from about 0.5 mm to about 1.3 mm, or from about 0.5 mm to about 1.2mm, or from about 0.6 mm to about 1.5 mm, or from about 0.6 mm to about1.4 mm, or from about 0.6 mm to about 1.3 mm, or from about 0.6 mm toabout 1.2 mm, or from about 0.7 mm to about 1.5 mm, or from about 0.7 mmto about 1.4 mm, or from about 0.7 mm to about 1.3 mm, or from about 0.7mm to about 1.2 mm, or from about 0.8 mm to about 1.5 mm, or from about0.75 mm to about 1.4 mm, or from about 0.75 mm to about 1.3 mm, or fromabout 0.75 mm to about 1.2 mm, and including all subranges andcombinations thereof.

In another aspect, the description provides an evaporative emissioncontrol canister system comprising one or more canisters including afuel-side adsorbent volume, and at least one vent-side parallel passageadsorbent volume (PPAV), wherein the at least one vent-side PPAVcomprises an outer surface and a plurality of parallel passages orchannels extending therethrough parallel to the outer surface, andwherein the parallel passages or channels are configured to have atleast one of an average channel hydraulic diameter (t_(c,Dh)) of lessthan or equal to 1.25 mm, a hydraulic diameter cell pitch (CP_(Dh)) ofless than or equal to 1.5 mm or a combination thereof.

In certain aspects, the description provides an evaporative emissioncontrol canister system comprising one or more canisters having aplurality of chambers, each chamber defining a volume, which are influid communication allowing a fluid or vapor to flow directionally fromone chamber to the next, and a chamber near a fuel vapor inlet (i.e.,fuel port or fuel tank port) includes a fuel-side adsorbent volume, andone chamber near a vent port includes a vent-side parallel passageadsorbent volume (PPAV), wherein the at least one vent-side PPAVcomprises an outer surface and a plurality of parallel passages orchannels extending therethrough parallel to the outer surface, andwherein the parallel passages or channels are configured to have atleast one of an average channel hydraulic diameter (t_(c,Dh)) of lessthan or equal to 1.25 mm, a hydraulic diameter cell pitch (CP_(Dh)) ofless than or equal to 1.5 mm or a combination thereof.

In other aspects or embodiments described herein, the descriptionprovides an evaporative emission control system comprising a fuel tankfor storing fuel, an engine having an air induction system and adaptedto consume fuel, and one or more canisters including a fuel-sideadsorbent volume and at least one vent-side PPAV, wherein the at leastone vent-side PPAV comprises an outer surface and a plurality ofparallel passages or channels extending therethrough parallel to theouter surface, and wherein the parallel passages or channels areconfigured to have at least one of an average channel hydraulic diameter(t_(c, Dh)) of less than or equal to 1.25 mm, a hydraulic diameter cellpitch (CP_(Dh)) of less than or equal to 1.5 mm or a combinationthereof, and

wherein the canister includes a fuel vapor inlet conduit connecting theevaporative emission control canister system to the fuel tank;

a fuel vapor purge outlet conduit connecting the evaporative emissioncontrol canister system to the air induction system of the engine; and

a vent conduit for venting the evaporative emission control canistersystem to the atmosphere and for admission of purge air to theevaporative emission control canister system, wherein the evaporativeemission control canister system is defined by a fuel vapor flow pathfrom the fuel vapor inlet conduit to the fuel-side adsorbent volumetoward the at least one PPAV and the vent conduit, and by an air flowpath from the vent conduit to the at least one PPAV toward the fuel-sideadsorbent volume and the fuel vapor purge outlet.

In any aspects or embodiments of the evaporative emission control systemor the evaporative emission control canister system described herein,the average channel hydraulic diameter (t_(c, Dh)) of the at least onevent-side PPAV as described herein is independently selected from, forexample, less than or equal to 1.25 mm, less than or equal to 1.20 mm,less than or equal to 1.10 mm, less than or equal to 1.0 mm; or fromabout 0.01 mm to about 1.25 mm, from about 0.1 mm to about 1.25 mm, fromabout 0.2 mm to about 1.25 mm, from about 0.3 mm to about 1.25 mm, fromabout 0.4 mm to about 1.25 mm; or from about 0.1 mm to about 1.20 mm,from about 0.1 mm to about 1.15 mm, from about 0.1 mm to about 1.10 mm,from about 0.1 mm to about 1.0 mm, from about 0.2 mm to about 1.20 mm,from about 0.2 mm to about 1.15 mm, from about 0.2 mm to about 1.1 mm,from about 0.2 mm to about 1.0 mm, from about 0.3 mm to about 1.25 mm,from about 0.3 mm to about 1.20 mm, from about 0.3 mm to about 1.15 mm,from about 0.3 mm to about 1.1 mm, from about 0.3 mm to about 1.0 mm,from about 0.4 mm to about 1.25 mm, from about 0.4 mm to about 1.20 mm,from about 0.4 mm to about 1.15 mm, from about 0.4 mm to about 1.1 mm,from about 0.4 mm to about 1.0 mm, from about 0.4 mm to about 0.95, orfrom about 0.4 mm to about 0.9 mm, and including all subranges andcombinations thereof.

In any aspects or embodiments of the evaporative emission control systemor the evaporative emission control canister system described herein,the hydraulic diameter cell pitch (CP_(Dh)) of the at least onevent-side PPAV as described herein is independently selected from, forexample, less than or equal to 1.50 mm, less than or equal to 1.40 mm,or less than or equal to 1.30 mm; or from about 0.5 mm to about 1.5 mm,or from about 0.5 mm to about 1.4 mm, or from about 0.5 mm to about 1.3mm, or from about 0.5 mm to about 1.2 mm, or from about 0.6 mm to about1.5 mm, or from about 0.6 mm to about 1.4 mm, or from about 0.6 mm toabout 1.3 mm, or from about 0.6 mm to about 1.2 mm, or from about 0.7 mmto about 1.5 mm, or from about 0.7 mm to about 1.4 mm, or from about 0.7mm to about 1.3 mm, or from about 0.7 mm to about 1.2 mm, or from about0.75 mm to about 1.5 mm, or from about 0.75 mm to about 1.4 mm, or fromabout 0.75 mm to about 1.3 mm, or from about 0.75 mm to about 1.2 mm,and including all subranges and combinations thereof.

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the PPAV further comprises at least one of thefollowing: (i) plurality channel width (t_(c, avg)) of less than about1.25 mm; (ii) plurality width cell pitch (CP_(tc)) of less than about1.5 mm; (iii) cell density of from about 285 to about 1000 cpsi; (iv)cell wall thickness of less than about 0.5 mm; (v) BWC of less thanabout 10 g/dL; (vi) an incremental adsorption capacity between 5% and50% n-butane at 25 C of less than about 50 g/L; or (vii) a combinationthereof. The features (i)-(vii) are contemplated in all combinationsdescribed herein with any of the options described above for t_(c, Dh)and/or CP_(Dh).

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the plurality channel width (t_(c, avg)) of thePPAV is, for example, less than about 1.25 mm, less than about 1.20 mm,less than about 1.15 mm, less than about 1.1 mm, less than 1.0 mm; orfrom about 0.1 mm to about 1.25 mm, from about 0.1 mm to about 1.20 mm,from about 0.1 mm to about 1.15 mm, from about 0.1 mm to about 1.10 mm,from about 0.1 mm to about 1.0 mm; or from about 0.2 mm to about 1.20mm, from about 0.2 mm to about 1.15 mm, from about 0.2 mm to about 1.1mm, from about 0.2 mm to about 1.0 mm; or from about 0.3 mm to about1.25 mm, from about 0.3 mm to about 1.20 mm, from about 0.3 mm to about1.15 mm, from about 0.3 mm to about 1.1 mm, from about 0.3 mm to about1.0 mm; or from about 0.4 mm to about 1.25 mm, from about 0.4 mm toabout 1.20 mm, from about 0.4 mm to about 1.15 mm, from about 0.4 mm toabout 1.1 mm, from about 0.4 mm to about 1.0 mm, or from about 0.4 mm toabout 0.9 mm, and including all subranges and combinations thereof.

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the plurality width cell pitch (CP_(tc)) of thePPAV, which is the average of the plurality of channel widths ofchannels of approximately the same cross-sectional dimensions, and notincluding peripheral channels (i.e., peripheral cells) in thecross-section, plus the average channel wall thickness (excluding theouter skin wall thickness)) is, for example, less than 1.6 mm, less than1.55 mm, 1.5 mm, less than about 1.45 mm, less than about 1.4 mm, lessthan about 1.35 mm, less than about 1.3, less than about 1.25 mm; fromabout 0.5 mm to about 1.5 mm, or from about 0.5 mm to about 1.4 mm, orfrom about 0.5 mm to about 1.3 mm, or from about 0.5 mm to about 1.2 mm,or from about 0.6 mm to about 1.5 mm, or from about 0.6 mm to about 1.4mm, or from about 0.6 mm to about 1.3 mm, or from about 0.6 mm to about1.2 mm, or from about 0.7 mm to about 1.5 mm, or from about 0.7 mm toabout 1.4 mm, or from about 0.7 mm to about 1.3 mm, or from about 0.7 mmto about 1.2 mm, or from about 0.75 mm to about 1.5 mm, or from about0.75 mm to about 1.4 mm, or from about 0.75 mm to about 1.3 mm, fromabout 0.75 mm to about 1.25 mm or from about 0.75 mm to about 1.2 mm,and including all subranges and combinations thereof.

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the cell density (i.e., channels or cells ifviewed in cross-section per square inch (“cpsi”) of the PPAV is, forexample, from about 285 to about 1000 cpsi, from about 300 to about 1000cpsi, from about 325 to about 1000 cpsi, from about 350 to about 1000cpsi, from about 375 to about 1000 cpsi, from about 400 to about 1000cpsi, from about 425 to about 1000 cpsi, from about 450 to about 1000cpsi, from about 500 to about 1000 cpsi, from about 550 to about 1000cpsi, from about 600 to about 1000 cpsi; or from 300 to about 950 cpsi,from 300 to about 900 cpsi, from about 300 to about 850 cpsi, from about300 to about 800 cpsi; or from about 400 to about 900 cpsi, from about400 to about 850 cpsi, from about 400 to about 800 cpsi, and includingall subranges and combinations thereof.

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the cell wall thickness of the PPAV is, forexample, from 0.1 mm to about 0.5 mm, from about 0.1 mm to about 0.45mm; or from about 0.15 mm to about 0.5 mm, 0.15 to about 0.4 mm; or fromabout 0.2 mm to about 0.5 mm; or from about 0.2 mm to about 0.45 mm, andincluding all subranges and combinations thereof. The average channelwall thickness is determined as described herein.

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the BWC (g/dL) of the PPAV is, for example,less than about 9.5, less than about 9.0, less than about 8.5, less thanabout 8.0, less than about 7.5, less than about 7.0, less than about6.5, less than about 6.0, less than about 5.5, less than about 5.0, lessthan about 4.5, less than about 4.0, less than about 3.5, less thanabout 3.0, less than about 2.5, less than about 2.0 g/dL, less thanabout 1.5 g/dL, less than about 1.0 g/dL, or less than about 0.5 g/dL;or from about 0.5 to about 10 g/dL, from about 0.5 to about 9 g/dL, fromabout 0.5 to about 8 g/dL, from about 0.5 to about 7 g/dL, from about0.5 to about 6 g/dL, from about 0.5 to about 5 g/dL, from about 0.5 toabout 4 g/dL, from about 0.5 to about 3 g/dL, from about 0.5 to about 2g/dL, from about 0.5 to about 1 g/dL; or from about 1 to about 10 g/dL,from about 1 to about 9 g/dL, from about 1 to about 8 g/dL, from about 1to about 7 g/dL, from about 1 to about 6 g/dL, from about 1 to about 5g/dL, from about 1 to about 4 g/dL, from about 1 to about 3 g/dL, fromabout 1 to about 2 g/dL; or from about 2.0 to about 10, from about 2.0to about 9.5, from about 2.0 to about 9.0, from about 2.0 to about 8.5,from about 2.0 to about 8.0, from about 2.0 to about 7.5, from about 2.0to about 7.0, from about 2.0 to about 6.5, from about 2.0 to about 6.0g/dL, from about 2.0 to about 5.5 g/dL, from about 2.0 to about 5.0g/dL, from about 2.0 to about 4.5 g/dL; or from about 2.5 to about 10,from about 2.5 to about 9.5, from about 2.5 to about 9.0, from about 2.5to about 8.5, from about 2.5 to about 8.0, from about 2.5 to about 7.5,from about 2.5 to about 7.0, from about 2.5 to about 6.5, from about 2.5to about 6.0 g/dL, from about 2.5 to about 5.5 g/dL, from about 2.5 toabout 5.0 g/dL, from about 2.5 to about 4.5 g/dL; or from about 3.0 toabout 10, from about 3.0 to about 9.5, from about 3.0 to about 9.0, fromabout 3.0 to about 8.5, from about 3.0 to about 8.0, from about 3.0 toabout 7.5, from about 3.0 to about 7.0, from about 3.0 to about 6.5,from about 3.0 to about 6.0 g/dL, from about 3.0 to about 5.5 g/dL, fromabout 3.0 to about 5.0 g/dL, or from about 3.0 to about 4.5 g/dL,including all subranges and combinations thereof.

Unless specified otherwise, BWC is determined in accordance with themethod described herein. In any of the aspects or embodiments describedherein, the PPAV (i.e., each article or part) as described herein has alength of between about 25 mm and 250 mm, or between about 50 mm and 150mm

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the incremental adsorption capacity (IAC)between 5% and 50% n-butane at 25° C. of the PPAV is, for example, lessthan about 50 g/L, less than about 45 g/L, less than about 40 g/L, lessthan about 35 g/L, less than about 30 g/L, less than about 25 g/L, lessthan about 20 g/L, less than about 15 g/L, less than about 10 g/L, lessthan about 5 g/L, less than about 4 g/L, less than about 3 g/L, lessthan about 2 g/L, or less than about 1 g/L; or from about 5 to about 50g/L, from about 5 to about 45 g/L, from about 5 to about 40 g/L, fromabout 5 to about 35 g/L, from about 5 to about 30 g/L, from about 5 toabout 25 g/L, from about 5 to about 20 g/L, from about 5 to about 15g/L, from about 5 to about 10 g/L; or from about 10 to about 50 g/L,from about 10 to about 45 g/L, from about 10 to about 40 g/L, from about10 to about 35 g/L, from about 10 to about 30 g/L, from about 10 toabout 25 g/L, from about 10 to about 20 g/L; or from about 15 to about50 g/L, from about 15 to about 45 g/L, from about 15 to about 40 g/L,from about 15 to about 35 g/L, from about 15 to about 30 g/L, from about15 to about 25 g/L, or from about 15 to about 20 g/L, and including allsubranges and combinations thereof.

In any of the aspects or embodiments of the evaporative emission controlsystem or the evaporative emission control canister system describedherein, has a two-day diurnal breathing loss (DBL) of no more than(i.e., less than or equal to) 50, 49, 48, 47, 46, 45, 44, 43, 42, 41,40, 39, 38, 37, 36, 35, 34, 33, 32, 31, 30, 29, 28, 27, 26, 25, 24, 23,22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3,2, 1 mg at no more than (i.e., less than or equal to) 350, 340, 330,320, 315, 310, 300, 290, 280, 270, 260, 250, 240, 230, 220, 210, 200,190, 180, 170, 160, 150, 140, 130, 120, 110, or 100 liters or no morethan (i.e., less than or equal to) 150, 140,130, 120, 110, 100, 90, 80,75, 70, 65, 60, 55, 50, 45, 40, 35, or 30 bed volumes (BV) of purgeapplied after a 40 g/hr butane loading step as determined by the 2012California Bleed Emissions Test Procedure (BETP).

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the PPAV comprises a channel having a width ofless than 1.25 mm, and a cell pitch of less than 1.5 mm. In certainembodiments, the PPAV demonstrates low vapor release properties asmeasured by an incremental adsorption capacity between 5 and 50%n-butane at 25° C. of less than 50 g/L between vapor concentration of 5vol % and 50 vol % n-butane.

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the PPAV has a feature as exemplified by theexperimental results provided herein, including, e.g., a numerical rangebased on data in the experimental results.

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the PPAV is in the form of a prism, e.g.,circular (i.e., cylinder), square, rectangular, triangular, pentagonal,etc., and as such, the parallel passages extend internally along thelength of the prism parallel to each other and parallel to the outersurface.

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the PPAV comprises an adsorbent materialderived from at least one of wood, wood dust, wood flour, cottonlinters, peat, coal, coconut, lignite, carbohydrates, petroleum pitch,petroleum coke, coal tar pitch, fruit pits, fruit stones, nut shells,nut pits, sawdust, palm, vegetables, synthetic polymer, natural polymer,lignocellulosic material, or a combination thereof. In any of theaspects or embodiments described herein, the PPAV comprises an adsorbentmaterial derived from wood or wood dust.

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the PPAV includes an adsorbent such asactivated carbon or carbon charcoal.

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the PPAV comprises an adsorbent materialselected from the group consisting of activated carbon, carbon charcoal,zeolites, clays, porous polymers, porous alumina, porous silica,molecular sieves, kaolin, titania, ceria, metal organic framework, andcombinations thereof.

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the PPAV comprises one or more binders, e.g.,an organic binder such as carboxymethyl cellulose (CMC) or an inorganicbinder, such as bentonite clay, or a combination of binders. In any ofthe aspects or embodiments described herein, the PPAV comprises one ormore cellulosic binders, e.g., carboxymethyl cellulose (CMC), and one ormore inorganic binders, e.g., a clay. In certain embodiments, the bindercomprises at least one of a clay or a silicate material. For example, incertain embodiments, the binder is at least one of zeolite clay,bentonite clay, montmorillonite clay, illite clay, French green clay,pascalite clay, redmond clay, terramin clay, living clay, Fuller's Earthclay, ormalite clay, vitallite clay, rectorite clay, cordierite, ballclay, kaolin or a combination thereof.

Additional potential binders include, thermosetting binders and hot-meltbinders. Thermosetting binders are compositions based on thermosettingresins which are liquid or solid at ambient temperature and inparticular those of urea-formaldehyde, melamine-urea-formaldehyde orphenol-formaldehyde type, resins of melamine-urea-formaldehyde typebeing preferred as well as emulsions of thermosetting (co)polymers inthe latex foam. Crosslinking agents can be incorporated in the mixture.Mention may be made, as example of crosslinking agents, of ammoniumchloride. Hot-melt binders are generally solid at ambient temperatureand are based on resins of hot-melt type. Use may also be made, asbinders, of pitch, tar or any other known binder.

In any of the embodiments described herein, the binder can comprise anaqueous soluble binders (e.g., polar binders), including but not limitedto cellulosic binders and related esters, including methyl and ethylcellulose and their derivatives, e.g., carboxymethyl cellulose (CMC),ethylcellulose, ethyl methyl cellulose, hydroxyethyl cellulose,hydroxypropyl cellulose (HPC), hydroxyethyl methyl cellulose,hydroxypropyl methyl cellulose (HPMC), ethyl hydroxyethyl cellulose,crystalline salts of aromatic sulfonates, polyfurfuryl alcohol,polyester, polyepoxide or polyurethane polymers etc.

In any of the embodiments described herein, the binder can comprise annon-aqueous binder, such as clays, phenolic resins, lignins,lignosulfonates, polyacrylates, poly vinyl acetates, polyvinylidenechloride (PVDC), ultra-high molecular weight polyethylene (UHMWPE),etc., fluoropolymer, e.g., polyvinylidene difluoride (PVDF),polyvinylidene dichloride (PVDC), a polyamide (e.g., Nylon-6,6′ orNylon-6), a high-performance plastic (e.g. polyphenylene sulfide),polyketones, polysulfones, and liquid crystal polymers, copolymers witha fluoropolymer (e.g. poly(vinylidene difluoride)),polytetrafluoroethylene (PTFE), fluorinated ethylene propylene, orperfluoroalkoxy alkanes), copolymers with a polyamide (e.g., Nylon-6,6′or Nylon-6), a copolymer with a polyimide, a copolymer with ahigh-performance plastic (e.g. polyphenylene sulfide) or a combinationthereof.

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the PPAV is produced from the bindercrosslinking of a ground precursor activated carbon material, whereinthe ground activated carbon material is in the form of a powder. Forexample, in certain embodiments, the shaped PPAV as described herein isproduced by taking a powdered activated carbon material and applying thecrosslinking binder technology of U.S. Pat. No. 6,472,343.

Alternatively, or in combination, an inorganic binder may be used. Theinorganic binder may be a clay or a silicate material. For example, thebinder may be at least one of Zeolite clay, Bentonite clay,Montmorillonite clay, Illite clay, French Green clay, Pascalite clay,Redmond clay, Terramin clay, Living clay, Fuller's Earth clay, Ormaliteclay, Vitallite clay, Rectorite clay, Cordierite, ball clay, kaolin or acombination thereof.

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the PPAV is formed into a monolith structure,e.g., a honeycomb configuration. In any of the aspects or embodimentsdescribed herein the PPAV monolith structure is prepared by a methodthat includes extruding a blend comprising an adsorbent material and abinder to form the parallel passage shape. In any of the aspects orembodiments of the PPAV, the evaporative emission control system or theevaporative emission control canister system described herein, the PPAV(e.g., PPAV monolith structure) is prepared by a method that includescoating the channels of a parallel passage structure scaffold with acoating layer comprising an adsorbent material. In any of the aspects orembodiments of the PPAV, the evaporative emission control system or theevaporative emission control canister system described herein, the PPAVmonolith structure is prepared by a method that includes coating thechannels of a parallel passage structure scaffold with a coating layercomprising a carbonaceous material that is converted in situ to anadsorbent by further thermal and/or chemical processing (e.g.,pyrolizing or chemical activation).

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the PPAV monolith structure is prepared by amethod that includes forming the parallel passage shape by stacking orwinding a corrugated sheet. In any of the aspects or embodimentsdescribed herein, the parallel passage shape is made from corrugatedsheet that contains adsorbent. In certain embodiments, the parallelpassage shape made from corrugated sheet that has adsorbent present in acoating layer. In any of the aspects or embodiments described herein,the PPAV or the at least one vent-side PPAV of the evaporative emissioncontrol system described herein, monolith structure is prepared by amethod that includes co-rolling a solid adsorbent sheet or layer withanother sheet or another material to create parallel passages. In any ofthe aspects or embodiments of the PPAV, the evaporative emission controlsystem or the evaporative emission control canister system describedherein, the PPAV monolith structure is prepared by a method thatincludes rolling a solid adsorbent sheet or layer that comprises ribs ornubs to create parallel passages. In any of the aspects or embodimentsdescribed herein, the adsorbent material is formed into a structure thatincludes a combination of any of the foregoing.

In any aspects or embodiments described herein, the evaporative emissioncontrol system or the evaporative emission control canister systemcomprises at least one additional vent-side adsorbent volume having anincremental adsorption capacity at 25° C. of from about 2 to about 35grams n-butane per liter (g/L) between vapor concentration of 5 vol %and 50 vol % n-butane. In any aspects or embodiments described herein,the evaporative emission control system or the evaporative emissioncontrol canister system comprises at least one vent-side adsorbentvolume having an incremental adsorption capacity at 25° C. of from about2 to about 30 grams n-butane per liter (g/L) between vapor concentrationof 5 vol % and 50 vol % n-butane. In any aspects or embodimentsdescribed herein, the evaporative emission control system or theevaporative emission control canister system comprises at least onevent-side adsorbent volume having an incremental adsorption capacity at25° C. of from about 2 to about 25 grams n-butane per liter (g/L)between vapor concentration of 5 vol % and 50 vol % n-butane. In anyaspects or embodiments described herein, the evaporative emissioncontrol system or the evaporative emission control canister systemcomprises at least one vent-side adsorbent volume having an incrementaladsorption capacity at 25° C. of from about 2 to about 20 grams n-butaneper liter (g/L) between vapor concentration of 5 vol % and 50 vol %n-butane.

In any aspects or embodiments described herein, the evaporative emissioncontrol system or the evaporative emission control canister systemcomprises at least one vent-side adsorbent volume having an incrementaladsorption capacity at 25° C. of from about 2 to about 15 grams n-butaneper liter (g/L) between vapor concentration of 5 vol % and 50 vol %n-butane. In any aspects or embodiments described herein, theevaporative emission control system or the evaporative emission controlcanister system comprises at least one vent-side adsorbent volume havingan incremental adsorption capacity at 25° C. of from about 2 to about 10grams n-butane per liter (g/L) between vapor concentration of 5 vol %and 50 vol % n-butane.

In any aspects or embodiments described herein, the evaporative emissioncontrol system or the evaporative emission control canister systemcomprises at least one vent-side adsorbent volume having an incrementaladsorption capacity at 25° C. of from about 2 to about 5 grams n-butaneper liter (g/L) between vapor concentration of 5 vol % and 50 vol %n-butane. In any aspects or embodiments described herein, theevaporative emission control system or the evaporative emission controlcanister system comprises at least one vent-side adsorbent volume havingan incremental adsorption capacity at 25° C. of from about 5 to about 30grams n-butane per liter (g/L) between vapor concentration of 5 vol %and 50 vol % n-butane.

In any aspects or embodiments described herein, the evaporative emissioncontrol system or the evaporative emission control canister systemcomprises at least one vent-side adsorbent volume having an incrementaladsorption capacity at 25° C. of from about 10 to about 30 gramsn-butane per liter (g/L) between vapor concentration of 5 vol % and 50vol % n-butane. In any aspects or embodiments described herein, theevaporative emission control system or the evaporative emission controlcanister system comprises at least one vent-side adsorbent volume havingan incremental adsorption capacity at 25° C. of from about 15 to about25 grams n-butane per liter (g/L) between vapor concentration of 5 vol %and 50 vol % n-butane.

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the PPAV has a gram-total (“g-tot”) BWC of lessthan 20 g, less than 19 g, less than 18 g, less than 17 g, less than 16g, less than 15 g, less than 14 g, less than 13 g, less than 12 g, lessthan 11 g, less than 10 g, less than 9 g, less than 8 g, less than 7 g,less than 6 g, less than 5 g, less than 4 g, less than 3 g, less than 2g or less than 1 g. In certain embodiments, the PPAV has a g-tot BWC offrom 0.1-20 g, from 0.1-20 g, from 0.1-19.5 g, from 0.1-18 g, from0.1-17.5 g, from 0.1-17 g, from 0.1-16.5 g, from 0.1-16 g, or from0.1-15.5 g, from 0.1-15 g, from 0.1-14.5 g, from 0.1-14 g, from 0.1-13.5g, from 0.1-13 g, from 0.1-12.5 g, from 0.1-12 g, from 0.1-11.5 g, orfrom 0.1-11 g, from 0.1-10.5 g, from 0.1-10 g, from 0.1-9.5 g, from0.1-9 g, from 0.1-8.5 g, from 0.1-8 g, from 0.1-7.5 g, from 0.1-7 g, orfrom 0.1-6.5 g, from 0.1-6 g, from 0.1-5.5 g, or from 0.1-5 g or a g-totBWC of one or more examples. As used herein, “gram-total BWC” refers tothe gram amount of butane purged from the PPAV.

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the PPAV as described herein has across-sectional hydraulic diameter of between 20 mm and 75 mm, orbetween about 29 mm and 41 mm.

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the PPAV as described herein has alength/hydraulic diameter ratio of between about 0.3 and 12.5, orbetween about 1.2 and 5.2.

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the PPAV as described herein has between about140 and 6450 channels (or cells in cross-section), or between about680-1365 channels (or cells in cross-section), inclusive of partialcells, e.g., cells in the periphery of the cross-section of acylindrical part). As would be readily apparent to the skilled artisan,the cells of the PPAV are representative of a cross-sectional view ofthe channels that extend along the interior length of the PPAV. As such,the number and density of cells is equivalent to the number and densityof channels.

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the PPAV as described herein has a totalchannel area of between about 60 mm² and 2760 mm², or between about 125mm² and 660 mm².

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the PPAV as described herein has flowrestriction at 40 lpm of between about 0.01 and 2.7 kPa) or betweenabout 0.03 and 0.9 kPa.

In any of the aspects or embodiments of the evaporative emission controlsystem or the evaporative emission control canister system describedherein, the canister system as described herein has adsorbentparticulate volumes that total between 1 liter and 5 liters.

In any of the aspects or embodiments of the PPAV, the evaporativeemission control system or the evaporative emission control canistersystem described herein, the PPAV comprises an adsorbent materialselected from the group consisting of activated carbon, carbon charcoal,zeolites, clays, porous polymers, porous alumina, porous silica,molecular sieves, kaolin, titania, ceria, metal organic framework, andcombinations thereof.

The adsorbent material may include any one or more of the abovefeatures, which can be combined in any number of ways according to thepresent description, and are expressly contemplated herein.

In additional aspects, the description provides evaporative emissioncontrol systems including one or more canisters comprising at least onePPAV as described herein.

FIG. 1 illustrates an exemplary embodiment of the evaporative emissioncontrol canister system 100 having adsorbent volumes in-series within asingle canister. Canister system 100 includes screens or foams 102, adividing wall 103, a fuel vapor inlet 104 from a fuel tank, a vent port105 opening to an atmosphere, a purge outlet 106 to an engine, afuel-side or initial adsorbent volume 201, and vent-side or subsequentadsorbent volume 202. The screens or foams 102 provide containment andsupport of the adsorbent volumes, as well as to serve as a distributor,to even the distribution of vapor flow into the adsorbent volumes. Thetwo chambers containing the adsorbent volumes 201 and 202 are separatedby the dividing wall 103 and connected for sequential vapor flow below asupport screen 102 by way of the passage 107, called the canisterplenum. Thus, in this example, the canister system defines a vapor flowpath from the fuel port 104, through the fuel-side adsorbent volume 201,the plenum space 107, vent-side adsorbent 202, to the vent port 105.When an engine is off, the fuel vapor from a fuel tank enters thecanister system 100 through the fuel vapor inlet 104. The fuel vapordiffuses or flows into the fuel-side or initial adsorbent volume 201,and then the vent-side or subsequent adsorbent volume 202 before beingreleased to the atmosphere through the vent port 105 of the canistersystem. Once the engine is turned on, ambient air is drawn into thecanister system 100 through the vent port 105. The purge air flowsthrough volumes 202 in the canister, and finally through the fuel-sideor initial adsorbent volume 201. This purge flow desorbs the fuel vaporadsorbed on the adsorbent volumes 202 through 201, before entering aninternal combustion engine through the purge outlet 106. As will beappreciated by the skilled artisan, FIGS. 2-8 present additionalexemplary canister systems that define adsorbent volumes in fluidcommunication along analogous fuel vapor/air flow paths.

In any of the embodiments of the evaporative emission control canistersystem described herein, the canister system may include more than onevent-side or subsequent adsorbent volume. For example, with reference toFIG. 2 , the fuel-side or initial adsorbent volume 201 may have anadditional or a plurality of vent-side (or subsequent) adsorbent volumes202 before the support screen 102 above the plenum 107, as shown in FIG.2 . Additional vent-side (or subsequent) adsorbent volumes 203 and 204may be found on the other side of the dividing wall.

Furthermore, in still additional embodiments, the canister system mayinclude more than one type of vent-side adsorbent volume, which can beindependently selected, and/or which is comprised in one or morecontainers. For example, as shown in FIG. 3 , an auxiliary chamber 300containing a vent-side adsorbent volume 301, such as the PPAV asdescribed herein, may be in-series in terms of air and vapor flow withthe main canister 101 containing multiple adsorbent volumes connectedfor vapor flow by way of a connecting hose or snorkel 108. As shown inFIG. 4 , the auxiliary chamber 300 may contain two vent-side adsorbentvolumes in-series 301 and 302, including, for example, at least one PPAVas described herein. The adsorbent volumes 301 and 302 may also becontained within in-series chambers or auxiliary canisters, rather thanthe single chamber 300 of FIG. 4 .

FIGS. 5-8 illustrate additional exemplary canister systems contemplatedby the present disclosure. FIGS. 5 and 6 shows a system including a maincanister 101 comprising an initial (fuel-side) adsorbent volume 501 andsubsequent (vent-side) adsorbent volumes 202, 203 and 204. The systemincludes a connecting hose or snorkel 108 leading to a supplementalcanister 300 on the vent-side, which includes an additional vent-sideadsorbent volume 502, for example, a PPAV as described herein, prior tothe vent port 105. FIG. 7 shows a system having an initial (fuel-side)adsorbent volume 501 a subsequent adsorbent volume 202 in the maincanister 101, connected via connecting hoses 108 to supplementalcanisters 300 and 503 that include subsequent (vent-side) adsorbentvolumes 502, 504 prior to vent port 105. In an exemplary embodiment, atleast one of 502 or 504 is a PPAV as described herein. FIG. 8illustrates an example of a single canister 101 design that includes aninitial (fuel-side) adsorbent volume 501, plenum space 107 leading tosubsequent (vent-side) adsorbent volumes 203 and 204, a second plenumspace 109 leading to additional subsequent (vent-side) adsorbent volumes502 and 504 prior to vent port 105. In an exemplary embodiment, at leastone of 502 or 504 is a PPAV as described herein.

As used herein, the term “upstream” refers to a location/volume withinthe system flow path that comes into contact with a fluid, e.g. fuelvapor, prior to or before another location/volume of the system alongthe flow path in the same relative direction. The term “downstream”refers to a location/volume within the system flow path that comes intocontact with a fluid, e.g. fuel vapor, after or subsequent to anupstream location/volume of the system along the flow path in the samerelative direction. That is, when referring to the fuel vapor flow path,an upstream location/volume is located closer to the fuel vapor inletrelative to another location/volume.

The term “fuel-side adsorbent volume” is used in reference to a volumeof adsorbent material that is proximal to the fuel vapor source, andtherefore, earlier in the fuel vapor flow path relative to a subsequentadsorbent volume, which is necessarily positioned closer to the ventport (herein, a “vent-side adsorbent volume”). As the skilled artisanwould appreciate, during a purge cycle, a vent-side or subsequentadsorbent volume(s) is contacted earlier in the purge air flow path. Forconvenience, the fuel-side adsorbent may be referred to as the “initialadsorbent volume” because it is positioned upstream in the fuel vaporflow path relative to the vent-side or subsequent adsorbent volume butthe initial adsorbent volume is not necessarily required to be the firstadsorbent volume in the canister.

In any of the aspects or embodiments of the evaporative emission controlsystem or the evaporative emission control canister system describedherein, the canister(s) can further comprise additional adsorbentvolumes as described herein, e.g., at least one adsorbent volume in achamber nearest to the fuel tank (i.e., fuel-side adsorbent volume),and/or at least one adsorbent volume closer to the outlet to theatmosphere (i.e., subsequent or vent-side adsorbent volume), including aPPAV as described herein.

In an additional embodiment, the disclosure provides an evaporativeemission control canister system comprising one or more canisters havinga plurality of chambers, each defining a volume, which are connected orin fluid communication permitting a fluid (e.g., air, gas or fuel vapor)to flow directionally and sequentially from one chamber to the next,wherein at least one chamber comprises a PPAV as described herein. Incertain embodiments, canister system comprises at least one additionaladsorbent volume. In certain embodiments, the adsorbent volumes arelocated within a single canister or within a plurality of canisters thatare connected to permit sequential contact by the fuel vapor.

In any of the aspects or embodiments of the evaporative emission controlsystem or the evaporative emission control canister system describedherein, the PPAV as described herein is incorporated into a vent-sidevolume in a 2.1 liter test canister having the dimensions as describedherein and demonstrates two-day DBL bleed emissions performance (secondday diurnal breathing loss (DBL) emissions) of about 100 mg or less,about 90 mg or less, about 80 mg or less, about 70 mg or less, about 60mg or less, about 50 mg or less, about 40 mg or less, about 30 mg orless, about 20 mg or less, or about 10 mg or less.

In any of the aspects or embodiments of the evaporative emission controlsystem or the evaporative emission control canister system describedherein, demonstrates two-day DBL bleed emissions performance of fromabout 10 mg to about 100 mg, from about 10 mg to about 90 mg, from about10 mg to about 80 mg, from about 10 mg to about 70 mg, from about 10 mgto about 60 mg, from about 10 mg to about 50 mg, from about 10 mg toabout 40 mg, from about 10 mg to about 30 mg, from about 10 mg to about20 mg, from about 15 mg to about 100 mg, from about 15 mg to about 90mg, from about 15 mg to about 80 mg, from about 15 mg to about 70 mg,from about 15 mg to about 60 mg, from about 15 mg to about 50 mg, fromabout 15 mg to about 40 mg, from about 15 mg to about 30 mg, from about15 mg to about 20 mg, from about 20 mg to about 100 mg, from about 20 mgto about 90 mg, from about 20 mg to about 80 mg, from about 20 mg toabout 70 mg, from about 20 mg to about 60 mg, from about 20 mg to about50 mg, from about 20 mg to about 40 mg, from about 20 mg to about 30 mg,from about 30 mg to about 100 mg, from about 30 mg to about 90 mg, fromabout 30 mg to about 80 mg, from about 30 mg to about 70 mg, from about30 mg to about 60 mg, from about 30 mg to about 50 mg, from about 30 mgto about 40 mg, from about 40 mg to about 100 mg, from about 40 mg toabout 90 mg, from about 40 mg to about 80 mg, from about 40 mg to about70 mg, from about 40 mg to about 60 mg, from about 40 mg to about 50 mg,from about 50 mg to about 100 mg, from about 50 mg to about 90 mg, fromabout 50 mg to about 80 mg, from about 50 mg to about 70 mg, from about50 mg to about 60 mg, from about 60 mg to about 100 mg, from about 60 mgto about 90 mg, from about 60 mg to about 80 mg, from about 60 mg toabout 70 mg, from about 70 mg to about 100 mg, from about 70 mg to about90 mg, from about 70 mg to about 80 mg, from about 80 mg to about 100mg, from about 80 mg to about 90 mg, or from about 90 mg to about 100mg, including all values and ranges overlapping, subsumed.

In any of the aspects or embodiments of the evaporative emission controlsystem or the evaporative emission control canister system describedherein comprising a PPAV as described herein provides the above two-dayDBL bleed emissions performance at no more than 210 liters (i.e., 100BV) or no more than 315 liters (i.e., 150 BV) of purge applied after a40 g/hr butane loading step as determined by the 2012 BETP.

In any of the aspects or embodiments of the evaporative emission controlsystem or the evaporative emission control canister system describedherein, the evaporative emission control canister system comprises atleast one fuel-side adsorbent volume and at least one subsequent (i.e.,vent-side) adsorbent volume, wherein at least one of the at least onefuel-side adsorbent volume or at least one subsequent adsorbent volumeincludes a PPAV as described herein.

In any of the aspects or embodiments of the evaporative emission controlsystem or the evaporative emission control canister system describedherein, the evaporative emission control canister system furthercomprises a heating unit or a means to add heat through electricalresistance or heat conduction.

In any of the aspects or embodiments of the evaporative emission controlsystem or the evaporative emission control canister system describedherein, the evaporative emission control canister system comprises oneor more vent-side adsorbent volumes having a substantially uniform cellstructure at or near the end of the fuel vapor flow path.

In certain embodiments, the at least one fuel-side or initial adsorbentvolume and the at least one vent-side or subsequent adsorbent volume (orvolumes) are in vaporous or gaseous communication and define an air andvapor flow path therethrough. The air and vapor flow path permits orfacilitates directional air or vapor flow or diffusion between therespective adsorbent volumes in the canister system. For example, theair and vapor flow path facilitates the flow or diffusion of fuel vaporfrom the at least one fuel-side or initial adsorbent volume to the atleast one vent-side or subsequent adsorbent volume (or volumes),including a PPAV as described herein.

In any of the aspects or embodiments of the evaporative emission controlsystem or the evaporative emission control canister system describedherein, the at least one fuel-side or initial adsorbent volume and theat least one vent-side or subsequent adsorbent volume(s) may be locatedwithin a single canister, separate canisters or a combination of both.For example, in certain embodiments, the system comprises one or morecanisters comprising a fuel-side or initial adsorbent volume, and one ormore vent-side or subsequent adsorbent volumes, wherein the vent-side orsubsequent adsorbent volumes are connected to the fuel-side initialadsorbent volume such that they are in vaporous or gaseous communicationforming a vapor flow path, and allowing air and/or vapor to flow ordiffuse therethrough, and wherein at least one venti-side adsorbentvolume is a vent-side PPAV as described herein. In certain aspects, thecanister permits sequential contact of the adsorbent volumes by air orfuel vapor.

In additional embodiments, the evaporative emission control canistersystem comprises a canister comprising an initial adsorbent volume, andone or more subsequent adsorbent volumes connected to one or moreseparate canisters comprising at least one additional subsequentadsorbent volume, including a vent-side PPAV as described herein,wherein the subsequent adsorbent volumes are connected to the initialadsorbent volume such that they are in vaporous or gaseous communicationforming a vapor flow path, and allowing air and/or fuel vapor to flow ordiffuse therethrough.

In any of the aspects or embodiments of the evaporative emission controlsystem or the evaporative emission control canister system describedherein, the evaporative emission control canister system comprises oneor more canisters comprising a fuel-side or an initial adsorbent volume,and one or more vent-side PPAV comprising an outer surface and aplurality of parallel passages or channels extending therethroughparallel to the outer surface, and wherein the parallel passages orchannels are configured to have at least one of an average channelhydraulic diameter (t_(c,Dh)) of less than or equal to 1.25 mm, ahydraulic diameter cell pitch (CP_(Dh)) of less than or equal to 1.5 mmor a combination thereof, and at least one of: (i) plurality channelwidth (t_(c, avg)) of less than about 1.25 mm; (ii) plurality channelwidth cell pitch t_(c, avg)) of (CP less than about 1.5 mm; (iii) celldensity of from about 285 to about 1000 cpsi; (iv) cell wall thicknessof less than about 0.5 mm; (v) BWC of less than about 10 g/dL; (vi) anincremental adsorption capacity between 5% and 50% n-butane at 25 C ofless than about 50 g/L; or (vii) a combination thereof, wherein thefuel-side adsorbent volume and the PPAV are in vaporous or gaseouscommunication forming a vapor flow path allowing air and/or fuel vaporto flow or diffuse therethrough.

In certain embodiments, the evaporative emission control canister systemhas a two-day diurnal breathing loss (DBL) of no more than 50, 40, 30,20, or 10 mg at no more than 315, 300, 290, 280, 270, 260, 250, 240,230, 220, 210, 200, 190, 180, 170, 160, 150, 140, 130, 120, 110, or 100liters of purge or no more than 150, 140, 130, 120, 110, 100, 90, 80,75, 70, 65, 60, 55, 50, 45, 40, 35 or 30 bed volumes (BV) applied aftera 40 g/hr butane loading step as determined by the 2012 California BleedEmissions Test Procedure (BETP).

In any of the aspects or embodiments of the evaporative emission controlsystem or the evaporative emission control canister system describedherein, the evaporative emission control canister system comprises acanister comprising a fuel-side or an initial adsorbent volume, and aPPAV, wherein the PPAV is a monolith such as a honeycomb, having anaverage channel hydraulic diameter of less than 1.25 mm and an hydraulicdiameter cell pitch of less than 1.5 mm. In certain embodiments theplurality of channels of approximately the same cross-sectionaldimensions, and not including peripheral channels in the cross-section,have a channel width plurality less than 1.25 mm and a plurality widthcell pitch of less than 1.5 mm.

In any of the aspects or embodiments of the evaporative emission controlsystem or the evaporative emission control canister system describedherein, the fuel-side or initial adsorbent volume is the first and/orsecond adsorbent volume, as such, the vent-side or subsequent adsorbentvolumes, including a PPAV as described herein, are downstream in thefluid flow path towards the vent port whether in the same or a separatecanister or both.

In any of the aspects or embodiments of the evaporative emission controlsystem or the evaporative emission control canister system describedherein, the disclosure provides an evaporative emission control canistersystem comprising one or more canisters having a plurality of chambers,each chamber defining a volume, which are in fluid communicationallowing a fluid or vapor to flow directionally from one chamber to thenext, and at least one chamber comprises at least one parallel passageadsorbent volume (PPAV), wherein the at least one PPAV has anincremental adsorption capacity (IAC) at 25° C. of less than 35 g/Lbetween vapor concentrations of 5 vol % and 50 vol % n-butane, anaverage channel hydraulic diameter of less than 1.25 mm, and anhydraulic diameter cell pitch (which is of the sum of the average cellchannel hydraulic diameter plus the average cell wall thickness(excluding the outer skin wall thickness)) of less than 1.5 mm.

In any of the aspects or embodiments of the evaporative emission controlsystem or the evaporative emission control canister system describedherein, the disclosure provides an evaporative emission control canistersystem including one or more canisters comprising at least one fuel-sideadsorbent volume; and at least one vent-side at least one parallelpassage adsorbent volume (PPAV), wherein the at least one PPAV has anincremental adsorption capacity (IAC) at 25° C. of less than 35 g/Lbetween vapor concentrations of 5 vol % and 50 vol % n-butane, anaverage channel hydraulic diameter of less than 1.25 mm, and anhydraulic diameter cell pitch of less than 1.5 mm.

In any of the aspects or embodiments of the evaporative emission controlsystem or the evaporative emission control canister system describedherein, the disclosure provides an evaporative emission control canistersystem including one or more canisters comprising at least one fuel-sideadsorbent volume; and at least one vent-side at least one parallelpassage adsorbent volume (PPAV), wherein the at least one PPAV has anincremental adsorption capacity (IAC) at 25° C. of less than 35 g/Lbetween vapor concentrations of 5 vol % and 50 vol % n-butane, anaverage channel hydraulic diameter (t_(c,Dh)) of less than 1.25 mm, andan hydraulic diameter cell pitch (CP_(Dh)) of less than 1.5 mm.

In any of the aspects or embodiments of the evaporative emission controlsystem or the evaporative emission control canister system describedherein, the disclosure provides an evaporative emission control canistersystem comprising one or more canisters having a plurality of chambers,each chamber defining a volume, which are in fluid communicationallowing a fluid or vapor to flow directionally from one chamber to thenext, and at least one chamber comprises at least one parallel passageadsorbent volume (PPAV) as described herein, wherein the at least onePPAV has an average channel hydraulic diameter of less than 1.25 mm, anincremental adsorption capacity (IAC) at 25° C. of less than 50 g/Lbetween vapor concentrations of 5 vol % and 50 vol % n-butane, aplurality of channel width (t_(c, avg)) of less than 1.25 mm, and aplurality width cell pitch (CP_(tc, avg)) (which is the average of theplurality of channel widths of channels of approximately the samecross-sectional dimensions, and not including peripheral channels orcells in the cross-section, plus the average channel wall thickness(excluding the outer skin wall thickness)) of less than 1.5 mm.

In any of the aspects or embodiments of the evaporative emission controlsystem or the evaporative emission control canister system describedherein, the disclosure provides an evaporative emission control canistersystem including one or more canisters comprising at least one fuel-sideadsorbent volume; and at least one vent-side parallel passage adsorbentvolume (PPAV), wherein the at least one vent-side PPAV has anincremental adsorption capacity (IAC) at 25° C. of less than 35 g/Lbetween vapor concentrations of 5 vol % and 50 vol % n-butane, aplurality of channel width (t_(c, avg)) of less than 1.25 mm, and aplurality width cell pitch (CP_(tc, avg)) of less than 1.5 mm.

In any of the aspects or embodiments of the evaporative emission controlsystem or the evaporative emission control canister system describedherein, the disclosure provides an evaporative emission control canistersystem including one or more canisters comprising at least one fuel-sideadsorbent volume; and at least one vent-side parallel passage adsorbentvolume (PPAV), wherein the at least one vent-side PPAV has anincremental adsorption capacity (IAC) at 25° C. of less than 25 g/Lbetween vapor concentrations of 5 vol % and 50 vol % n-butane, aplurality of channel width (t_(c, avg)) of less than 1.25 mm, and aplurality width cell pitch (CP_(tc, avg)) of less than 1.5 mm.

In another aspect, the disclosure provides an evaporative emissioncontrol system comprising a fuel tank for storing fuel; an engine havingan air induction system and adapted to consume the fuel; an evaporativeemission control canister system including one or more canisterscomprising a plurality of adsorbent volumes including at least onefuel-side adsorbent volume; and at least one vent-side parallel passageadsorbent volume (PPAV) as described herein, wherein the at least onevent-side PPAV has an average channel hydraulic diameter of less than1.25 mm, an incremental adsorption capacity (IAC) at 25° C. of less than50 g/L between vapor concentrations of 5 vol % and 50 vol % n-butane, anaverage channel hydraulic diameter (t_(c,Dh)) of less than 1.25 mm, andan hydraulic diameter cell pitch (CP_(Dh)) of less than 1.5 mm; a fuelvapor inlet conduit connecting the evaporative emission control canistersystem to the fuel tank; a fuel vapor purge conduit connecting theevaporative emission control canister system to the air induction systemof the engine; and a vent port for venting the evaporative emissioncontrol canister system and for admission of purge air to theevaporative emission control canister system, wherein the evaporativeemission control canister system is defined by: a fuel vapor flow pathfrom the fuel vapor inlet conduit through a plurality of adsorbents tothe vent port, and an air flow path from the vent port through theplurality of adsorbent volumes and the fuel vapor purge outlet.

In an additional aspect, the disclosure provides methods for reducingfuel vapor emissions in an evaporative emission control system, themethod comprising providing one or more canisters comprising a fuel-sideadsorbent volume and at least one parallel-passage adsorbent volume(PPAV), and contacting the fuel vapor with the adsorbent volumes),wherein the at least one vent-side PPAV has an average channel hydraulicdiameter of less than 1.25 mm, and an hydraulic diameter cell pitch ofless than 1.5 mm, and optionally, an incremental adsorption capacity(IAC) at 25° C. of less than 50 g/L between vapor concentrations of 5vol % and 50 vol % n-butane.

In an additional aspect, the disclosure provides methods for reducingfuel vapor emissions in an evaporative emission control system, themethod comprising providing one or more canisters comprising a pluralityof adsorbent volumes including at least one fuel-side adsorbent volume;and at least one vent-side parallel passage adsorbent volume (PPAV),wherein the at least one vent-side PPAV has an average channel hydraulicdiameter of less than 1.25 mm, a plurality of channel widths of lessthan 1.25 mm, and a plurality width cell pitch of less than 1.5 mm, andoptionally, an incremental adsorption capacity (IAC) at 25° C. of lessthan 50 g/L between vapor concentrations of 5 vol % and 50 vol %n-butane.

In any of the aspects or embodiments described herein, the at least oneparallel passage adsorbent volume, or at least one vent-side parallelpassage adsorbent volume has at least one of: an incremental adsorptioncapacity (IAC) at 25° C. of less than 50 g/L between vaporconcentrations of 5 vol % and 50 vol % n-butane, an average channelhydraulic diameter of less than 1.25 mm, and a hydraulic diameter cellpitch of less than 1.5 mm, or a combination thereof. In any of theaspects or embodiments described herein, the at least one parallelpassage adsorbent volume, or at least one vent-side parallel passageadsorbent volume has at least one of: an incremental adsorption capacity(IAC) at 25° C. of less than 50 g/L between vapor concentrations of 5vol % and 50 vol % n-butane, a plurality of channel widths of less than1.25 mm, and a plurality width cell pitch of less than 1.5 mm, or acombination thereof.

In any of the aspects or embodiments described herein, the evaporativeemission control canister system comprises at least one fuel-sideadsorbent volume, at least one vent-side PPAV, and optionally at leastone additional vent-side adsorbent volume.

In any of the aspects or embodiments described herein, the adsorbentvolumes are located within a single canister or within a plurality ofcanisters that are connected to permit sequential contact by the fuelvapor.

In any of the aspects or embodiments described herein, the at least onevent-side PPAV is an activated carbon honeycomb.

In any of the aspects or embodiments described herein, the at least oneadditional vent-side adsorbent volume is an activated carbon honeycomb.

In any of the aspects or embodiments described herein, the activatedcarbon is derived from a material including a member selected from thegroup consisting of wood, wood dust, wood flour, cotton linters, peat,coal, coconut, lignite, carbohydrates, petroleum pitch, petroleum coke,coal tar pitch, fruit pits, fruit stones, nut shells, nut pits, sawdust,palm, vegetables, synthetic polymer, natural polymer, lignocellulosicmaterial, and combinations thereof.

In any of the aspects or embodiments described herein, the form of theadsorbent includes a member selected from the group consisting ofgranular, pellet, spherical, honeycomb, monolith, pelletizedcylindrical, particulate media of uniform shape, particulate media ofnon-uniform shape, structured media of extruded form, structured mediaof wound form, structured media of folded form, structured media ofpleated form, structured media of corrugated form, structured media ofpoured form, structured media of bonded form, non-wovens, wovens, sheet,paper, foam, hollow-cylinder, star, twisted spiral, asterisk, configuredribbons, and combinations thereof.

In any of the aspects or embodiments described herein, the canistersystem further comprises a heat unit.

In any of the aspects or embodiments described herein, the evaporativeemission control canister system comprises at least one vent-sideparallel passage adsorbent volume (PPAV), wherein the at least one PPAVhas an average channel hydraulic diameter of less than 1.25 mm, and anhydraulic diameter cell pitch of less than 1.50 mm, wherein the at leastone vent-side PPAV optionally has an effective BWC of less than about 10g/dL, an effective incremental adsorption capacity at 25° C. of lessthan about 50 grams n-butane per liter (g/L) between vapor concentrationof 5 vol % and 50 vol % n-butane or a combination thereof.

Additional aspects and embodiments will be evident to the skilledartisan based on the description above in view of the examples thatfollow, which are expressly contemplated as being part of thedescription as though expressly set forth herein.

EXAMPLES

Determination of Apparent Density, BWC, and Powder Butane Activity

ASTM D2854 (may be used to determine the apparent density of particulateadsorbents, such as granular and pelletized adsorbents of the size andshape typically used for evaporative emission control for fuel systems.

ASTM D5228 may be used to determine the butane working capacity (BWC) ofthe adsorbent volumes containing particulate granular and/or pelletizedadsorbents. The butane retentivity is calculated as the difference, inunits of g/dL, between the volumetric butane activity (i.e., the g/ccapparent density multiplied by the g/100 g butane activity) and the g/dLBWC.

For powdered activated carbon ingredients for extrusion, a powder butaneactivity (“pBACT”) may be measured by any method known to those of skillin the art recognized as equivalent for ascertaining that value, i.e.,the equilibrated gram weight capacity of the oven dried powder samplewhen exposed to 1.00 atm partial pressure of n-butane, for the samplethermostatted at 25° C. One suitable alternative for pBACT, for example,is based on the ASTM 5228 method, as described in US 2019/0226426A1,which is incorporated herein by reference in its entirety.

A modified version of ASTM D5228 method may be used to determine thebutane working capacity (BWC) of particulate, honeycomb, monolith,and/or sheet adsorbent volumes. The modified ASTM D5228 method may alsobe used for particulate adsorbents, where the particulate adsorbentsinclude fillers, voids, structural components, or additives.Furthermore, the ASTM D5228 modified method may be used where theparticulate adsorbents are not compatible with the standard method ASTMD5228, e.g., a representative adsorbent sample may not be readily placedas the 16.7 mL fill in the sample tube of the test.

The modified version of ASTM D5228 method is as follows. The adsorbentsample (e.g., a PPAV honeycomb or monolith) is oven-dried for a minimumof three hours at 110±5° C., and then placed in desiccators to cooldown. The dry mass of the adsorbent sample is recorded. The mass of theempty testing assembly (which is 47 mm inside diameter×200 mm long) isdetermined before the adsorbent sample is assembled into a testingassembly. Then, the test assembly is installed into the flow apparatusand loaded with n-butane gas for a minimum of 25 minutes (±0.2 min) at abutane flow rate of 500 ml/min at 25° C. and 1 atm pressure. The testassembly is then removed from the BWC test apparatus. The mass of thetest assembly is measured and recorded to the nearest 0.001 grams. Thisn-butane loading step may be repeated for successive 5 minutes flowintervals until constant mass is achieved. In the examples describedherein, the time for loading and purging time was calculated based onpart volume. For example, the total butane load time for a 35 mmdiameter×150 mm long honeycomb was from 87 to 92 minutes. The testassembly may be a holder for a honeycomb or monolith part, for the caseswhere the volume may be removed and tested intact. Alternatively, thevolume may need to be a section of the canister system, or a suitablereconstruction of the volume with the contents appropriately oriented tothe gas flows, as otherwise encountered in the canister system.

The test assembly is reinstalled to the test apparatus and purged with 2liter/min dry air at 25° C. and 1 atm pressure for a set selected purgetime (±0.2 min) according to the formula:

Purge Time (min)=(719×Volume (ml))/(2000 (ml/min)).

The direction of the air purge flow in the BWC test is in the samedirection as the purge flow to be applied in the canister system. Afterthe purge step, the test assembly is removed from the BWC testapparatus. The mass of the test assembly is measured and recorded to thenearest 0.001 grams within 15 minutes of test completion.

The butane working capacity (BWC) of the adsorbent sample was determinedusing the following equation:

BWC (g/dL)=Amount of Butane Purged (g)/Nominal Adsorbent Volume (dL).wherein the Amount of Butane Purged=Mass of the test assembly afterloading−Mass of the test assembly after purge. For examples including acylindrical PPAV, the following calculations were also used:

-   -   Apparent Density (g/mL) is calculated as Volume (mL)/mass of        adsorbent (g);    -   Adsorbent Volume (ml) is calculated as π D_(o,c) (mm)²        L(mm)/4000;    -   Butane Activity (g/100 g) is calculated as, BACT (g/100        g)=amount of butane loaded (g)/(100×mass of adsorbent (g));    -   Butane Purge Ratio (%)=BPR (%) is calculated as, amount of        butane purged (g)/amount of butane loaded (g)×100.

Determination of Diurnal Breathing Loss (DBL) Emissions According to aBETP Test

The evaporative emission control systems in the examples were tested bya protocol that include the following. For tests with the type Acanister system, the defined 2.1 L canister that was used for generatingthe DBL emissions data was of the type illustrated in FIG. 5 . The threepellet bed volumes 501, 203, and 204 were located in a main canister101, containing 1.40 L, 0.40 L and 0.30 L of pellets, respectively. Theexample PPAV honeycomb was present as adsorbent volume 502 in anauxiliary canister 300, including seals around the cylinders for sealing(not shown in canister illustrations) and thin disks of non-adsorbentopen cell foam on each end of the honeycomb (102 in FIG. 5 ).

For tests with the type B canister system (examples are noted hereinwith a ‘B’ suffix), the adsorbent bed configuration was the same as withthe type A system, except that 1) a different, single grade of carbonpellets was used in the main canister, and 2) the two adsorbent volumes203 and 204 of FIG. 4 were configured as a single 0.70 L volume ofpellets, as illustrated in FIG. 6 . For the example noted as “12a+bB”,the canister system was type B, with the exception that there were twoauxiliary canisters in-series, as illustrated in FIG. 7 . The firstauxiliary canister 300 contained PPAV honeycomb 12 a as adsorbent volume502 and the in-series second auxiliary canister 503 contained PPAVhoneycomb 12 b as adsorbent volume 504, with seals (not shown) and, andwith non-adsorbent open cell foam disks 102 at each end of the two PPAVhoneycombs.

In the type A system, a 1.40 L of NUCHAR® BAX 1500 (Ingevity®, NorthCharleston, S.C., USA) as adsorbent volume 501, with about a 19.5 cmheight above the support screen 102 located above the plenum 107, plus a0.40 L adsorbent volume 203 of NUCHAR® BAX 1500 with about a 11.1 cmheight above the support screen 102 located above the plenum 107, andplus a 0.3 L adsorbent volume 204 of NUCHAR® BAX LBE with about a 8.4 cmheight above a support screen 102 between adsorbent volumes 203 and 204.The adsorbent volume 501 had an average width of 9.0 cm from thedividing wall 103 to the right side wall of the canister, and theadsorbent volumes 203 and 204 have average widths of about 4.5 cm fromthe dividing wall 103 to its left sidewall. Adsorbent volumes 501, 203,and 204 had similar depths (into the page in FIG. 5 ) of 8.0 cm. Eachadsorbent bed of pellets was filled with the dry-basis mass determinedby the apparent density that would meet the respective volume target(mass fill=AD×volume target). Table 1 describes the grade and propertiesof the main canister adsorbent volume fills. For type B canistersystems, the adsorbent volumes in the main canister were only filledwith NUCHAR® BAX 1100LD, as described in Table 1.

For tests with Type C canisters, the defined canister that was used forgenerating the DBL emissions data was of the type illustrated in FIG. 8. This canister system was a commercial canister used in Honda CR-VModel Year 2017 vehicles (Evap Family HHNXR01221SA/B). The Type Ccanister was used with the examples noted as 20 a+bC and 21 a+bC, Thetype C system had 1.86 L of NUCHAR® BAX 1100 LD (Ingevity®, NorthCharleston, S.C., USA) as adsorbent volume 501 with about a 22.6 cmheight above the support screen 102 located above the plenum 107, plus a0.26 L adsorbent volume 203 of NUCHAR® BAX 1100 LD with about a 7.8 cmheight above the support screen 102 located above the plenum 107, andplus a 0.23 L adsorbent volume 204 of NUCHAR® BAX LBE with about a 7.4cm height above a support screen 102 between adsorbent volumes 203 and204. The adsorbent volume 501 was cylindrical and had a diameter of 11.1cm, and the adsorbent volumes 203 and 204, also cylindrical, withaverage diameters of about 6.8 cm. Following air gap 109, was PPAVhoneycomb 20a (or 21a) as adsorbent volume 502 and the in-series secondPPAV honeycomb 20b (or 21b) as adsorbent volume 504, with seals (notshown) and with non-adsorbent open cell foam disks 102 at each end ofthe two PPAV honeycombs.

Each example canister system was uniformly preconditioned (aged) byrepetitive cycling of gasoline vapor adsorption using certified Tier 3fuel (8.7-9.0 RVP, 10 vol % ethanol) and 300 bed volumes of dry airpurge at 22.7 LPM based on the main canister (e.g., 630 liters for a 2.1L main canister). The gasoline vapor load rate was 40 g/hr and thehydrocarbon composition was 50 vol %, generated by heating two liters ofgasoline to about 38° C. and bubbling air through at 200 ml/min. Thetwo-liter aliquot of fuel was replaced automatically with fresh gasolineregularly to maintain an approximately constant vapor generation rateuntil 5000 ppm breakthrough as butane was detected by an FID (flameionization detector) or infrared detector. A minimum of 25 aging cycleswere used on a virgin canister. The gasoline working capacity (GWC) wasmeasured as the average weight gain of loaded vapors and loss of purgedvapors for the last 2-3 cycles and is reported as grams per liter ofadsorbent volumes in the canister system. In proceeding further tomeasure bleed emission performance, the GWC aging cycles were followedby a single butane adsorption/air purge step. Butane was loaded at 40g/hour at a 50 vol % concentration in air at one atm to 5000 ppmbreakthrough, followed by soaking for one hour, then purging with dryair for 21 minutes with a total purge volume attained by selecting theappropriate constant air purge rate for that period. The canister systemwas then soaked with the ports sealed for about 14-18 hrs at about 25°C. (where 12-36 hrs is the requirement for the soak time). For the DBLdata in FIGS. 17 through 22, 25-32, and 42-44 the total purge volumefollowing the above single butane adsorption loading was 210 L,equivalent, for example, to about 91-95 BV for a complete canistersystem that includes all adsorbent volumes present, e.g., the 2.1 Ladsorbent volume fills of the defined canister, plus a vent-sideactivated carbon honeycomb adsorbent 502 placed in the subsequentauxiliary canister 300, or two activated carbon honeycomb adsorbents 502and 504 placed in subsequent in-series auxiliary canisters 300 and 503.In these configurations, the volume to be added to the adsorbent pelletvolumes in the defined main canister was the caliper measureddimensional volume of the activated carbon honeycomb present withinauxiliary canister 300, plus, if present, the caliper-measureddimensional volume of the second activated carbon honeycomb within thein-series auxiliary canister 503.

For the DBL data in FIGS. 32 and 33 , the total purge volume ranged from210-310 liters, equivalent to about 94-138 BV for a complete canistersystem that includes all adsorbent volumes present. For the DBL data inFIGS. 34 and 35 , the total purge volume ranged from 124-210 liters,equivalent to about 50-85 BV for a complete canister system thatincludes all adsorbent volumes present.

The DBL emissions were subsequently generated by attaching the tank portof the example to a fuel tank filled with CARB LEV III fuel (6.9-7.2RVP, 10% ethanol). The canister system examples with the majority ofpellets present as BAX 1500 grade carbon in the main canister wereconnected to a 20 gallon tank (total volume) filled with 6.2 gallons ofliquid fuel (13.8 gal ullage). The canister system examples with BAX1100 LD in the main canister were connected to a 15 gallon tank (totalvolume) filled with 4.0 gallons of liquid fuel (11 gal ullage). The typeC canister system examples were connected to a 14 gallon tank (ratedvolume) filled with 5.6 gallons of liquid fuel.

Prior to attachment, the filled fuel tank had been stabilized at 18.3°C. for 18-20 hours while venting (where 12-36 hrs is the requirement ofthe soak time while venting). The tank and the canister system were thentemperature-cycled per CARB's two-day temperature profile, each day from18.3° C. to 40.6° C. over 11 hours, then back down to 18.3° C. over 13hours. Emission samples were collected from the example vent at 6 hoursand 12 hours during the heat-up stage into Kynar bags (to allow the fuelin the tank to reach peak temperature). The Kynar bags were filled withnitrogen to a known total volume based on pressure and then evacuatedinto a FID to determine hydrocarbon concentration. The FID wascalibrated with a precisely known-butane standard of about 5000 ppmconcentration. From the Kynar bag volume, the emissions concentration,and assuming an ideal gas, the mass of emissions (as butane) wascalculated. For each day, the mass of emissions at 6 hours and 12 hourswere added. Following CARB's protocol the day with the highest totalemissions was reported as “2-day emissions.” In all cases, exceptexample 24, the highest emissions were on Day 2. For example 24, the day1 emissions were 278 mg while the day 2 emissions were 178 mg. Thisprocedure is generally described in SAE Technical Paper 2001-01-0733,titled “Impact and Control of Canister Bleed Emissions,” by R. S.Williams and C. R. Clontz, and in CARB's LEV III BETP procedure (sectionD.12 in California Evaporative Emissions Standards and Test Proceduresfor 2001 and Subsequent Model Motor Vehicles, Mar. 22, 2012).

TABLE 1 Exemplary evaporative emission control canister systems. 7, 8,11, 13, 1⁹, 4⁹ EXAMPLE (PPAV in 1-6⁸ 14, 15, 16, 1R, 2R, 4R 20a + bC⁴,chamber 300) 17 22, 23, 24 9, 10 25 18, 19 9B,12a + bB³ 21a + bC⁴Canister System Type: A A A A A B C Pellet Type in FIG. 5 1 1 1 1 1 I¹I⁵ Volume 501, 1.40 L Pellet Type in Fig. 5 1 1 1 1 1 I² I⁶ Volume 203,0.40 L Pellet Type in FIG. 5 2 2 2 2 2 27 Volume 204, 0.30 L Pellet Type1 Properties: NUCHAR ® Pellet Grade BAX 1500 BAX 1100LD BAX 1100 LDApparent Density, g/mL; 0.282 0.289 0.285 0.278 0.285 0.316 0.322 ADButane Activity, g/100 g; 62.8 57.9 62.5 63.8 62.5 40.8 43.7 BACT ButaneActivity, g/dL; 17.7 16.7 17.8 17.7 17.8 12.9 14.1 VACT = AD × BACT BWC,g/dL 15.3 14.9 15.3 15.5 15.3 11.0 11.9 Butane Purge Ratio; BPR = 86.488.8 86.8 87.2 86.8 85.0 84.5 BWC/VACT × 100 Incremental Adsorption 73.074.1 79.9 78.2 79.9 56.3 58.9 Capacity 5-50%, g/L; IAC Pellet Type 2Properties: NUCHAR ® Pellet Grade BAXLBE — BAXLBE Apparent Density,g/mL; 0.374 0.370 0.374 0.370 0.370 — 0.382 AD Butane Activity, g/100 g;18.4 18.5 18.4 18.5 18.5 — 19.0 BACT Butane Activity, g/dL; 6.9 6.8 6.96.8 6.8 — 7.3 VACT = AD × BACT BWC, g/dL 6.1 6.1 6.1 6.1 6.1 — 6.6Butane Purge Ratio; BPR = 89.3 89.6 89.3 89.6 89.6 — 90.8 BWC/VACT × 100Incremental Adsorption 28.7 27.2 28.7 27.2 27.2 — 29.8 Capacity 5-50%,g/L; IAC ¹Pellet type in the 1.40 L volume 501 in FIGS. 6 and 7. ²Pellettype in a single, 0.70L volume 202 in FIGS. 6 and 7. ³Example 12a + bBin chambers 300 + 503 in FIG. 7 ⁴Examples 20a + bC and 21a + bC as PPAV502 + 504 in Fig QX4 ⁵Pellet type in the 1.86 L volume 501 in FIG. 8⁶Pellet type in the 0.26 L volume 203 in FIG. 8 ⁷Pellet type in the 0.23L volume 204 in FIG. 8 ⁸In Table 12 Effect of Purge LEV II SystemExamples 1 and 4, these are the pellet properties for the test only at210 L ⁹In Table 12 Effect of Purge LEV II System Examples 1 and 4, theseare the pellet properties for the tests at 256 and 310 L

Determination of Flow Restriction

For the honeycomb PPAV monoliths, the flow restriction (kPa) wasmeasured from 10-100 slpm at 10 slpm increments using the PPAV holdernormally otherwise used for canister system tests (e.g., holder 300shown in FIGS. 3-5 ). A correction to the flow restriction was appliedfor the pressure drop of the empty holder at the same flow rate. Aquadratic equation was employed for fitting the flow restriction data asa function of flow rate. The data are reported here as the flowrestrictions calculated at 40 slpm and at flows equivalent to asuperficial velocity of 46 cm/s by taking into account thecross-sectional area of the monolith as measured by calipers fordiameter. For the canister system that includes the main canister andPPAV monolith-containing auxiliary canister(s) on the vent-side, flowrestrictions were measured under pressurized load flow from the fueltank port 104 to the vent port 105 with the engine purge port 106 closedin FIGS. 3-5 (“system load dP”) and were measured under pressurizedpurge flow from the vent port 105 to the engine port 106 with the fueltank port 104 closed (system purge dP). A quadratic equation wasemployed for fitting the flow restriction data as a function of flowrate and the system load and purge dP is reported here at the calculated40 slpm.

Measurement of Dynamic Butane Adsorption Capacity

The PPAV honeycomb monolith part samples were placed inside acylindrical sample holder oriented in the vertical direction, and testedin a 25 C chamber for dynamic adsorption capacity (DAC) according to aload-purge-reload protocol (see US 2020/0018265A1, which is incorporatedherein by reference in its entirety).

In DAC testing, the sample and its holder were initially weighed, andthen loaded with a 25 C, 1:1 n-butane:N₂ test gas flow rate (50 vol %n-butane) of 134 mL/min (9.5 g/hour of butane flow), until saturation.The direction of flow was downward from the top of the sample holder tothe bottom. The gas composition of the effluent flow from the sampleholder was monitored by an Emerson X-STREAM IR Spectrometer. After thesaturation step, the sample and its holder were reweighed and thenbriefly purged with N₂ at 100 mL/min for 10 minutes in the same flowdirection as saturation. After the brief purge, the sample and itsholder were reweighed and then desorbed with a 10 L/min flow of N₂ for15 minutes in the opposite flow as the initial saturation flow directionrelative to the sample (i.e., 10 L/min purge gas flow was downward, butwith the sample flipped 180°). In the following step after a finalstandard 5-minute pause for mechanical adjustments, the gas compositionwas switched to a mixture of 0.5 vol % butane in N₂ at 134 ml/min (0.1g/hour of butane flow), and this loading step was also conducted as adownflow, in the same flow direction as the initial saturation relativeto the sample (i.e., 0.5 vol % butane flow was downward, but with thesample flipped again 180°, to its original orientation). Thebreakthrough curve of adsorbate in the effluent stream was recordedusing the IR spectrometer described above.

The key measured response of the PPAV part in the DAC test is theeffluent concentration as the sample undergoes progressive saturationacross the length of the adsorbent volume, including any backgroundseepage of adsorbate emissions, called bleedthrough, and thebreakthrough of the wavefront of adsorbate concentration gradient thatpasses through the volume, known as the mass transfer zone (MTZ). Thus,this progression of adsorption has three periods: 1) An initial periodof bleedthrough with relatively steady zero or low concentration ofadsorbate in the effluent as all, or nearly all, inlet adsorbate isremoved by the adsorbent bed, 2) a period of accelerated and thendecelerated rise in adsorbate concentration in the effluent stream whenthere is breakthrough of the MTZ, and 3) a final period fullequilibrated saturation of the adsorbate bed, subsequent to the MTZbreakthrough, as the adsorbent bed across its length reaches thermal andconcentration equilibration with the influent stream conditions. Astypical in the art, the MTZ wavefront is quantified by the point of 5%of the influent adsorbate concentration detected in the effluent and thepoint of 95% of the influent adsorbate concentration detected in theeffluent. A highly efficient adsorbent bed has a sharp MTZ such thatthere is minimal mass of adsorbate in the effluent prior to saturation,i.e., a greater percentage of the adsorbent beds potential capacity forthe adsorbate is utilized as compared with the losses in the effluentfor a given point of MTZ concentration breakthrough (“BT”). Prior to MTZbreakthrough, there can be a significant amount of bleedthrough if theadsorbent bed has a residual heel of adsorbate from a previous contactwith adsorbate such as from sequential adsorption and purge steps,allowing an unimpeded flow of influent adsorbate to pass through thebed.

For a virgin PPAV part (i.e., free of adsorbate at t=0 time), theeffluent curve typically has the appearance of FIG. 14 . Key points ofthe effluent curve occur at the time of 5% influent adsorbateconcentration in the effluent beyond the initial bleedthroughconcentration, t_(v5%), and the time t_(v95%), when the effluentadsorbate concentration reaches 95% of the difference between theinitial bleedthrough concentration and the influent adsorbateconcentration, “the time for 95% BT beyond initial bleedthrough”. (For avirgin adsorbent bed, the bleedthrough is about zero, so that t_(v5%) isessentially the time of 5% of the influent measured in the effluent, andt_(v95%) is the time of 95% of the influent concentration present in theeffluent). At t_(v5)%, from a mass balance on the influent and effluentrates of adsorbate flow over time, the cumulative mass adsorbed by thebed is m_(ads, V5%) (a portion of the shaded area in FIG. 14 , betweent=0 and t_(v5%)) and the cumulative mass of adsorbate in the effluent ism_(efl, V5%). An efficiency of adsorption for that initial period,DAE_(V5%), is the ratio of the amount adsorbed up until that time,m_(ads, V5%), and the total influent mass of adsorbate delivered to theadsorbent bed over that time period (e.g., the ratio of m_(ads, V5%)over m_(efl, V5%)+m_(ads, V5%)). By time t_(v95%), with the passage ofthe majority of the MTZ into the bed effluent, the cumulative massadsorbed by the bed is m_(ads, V95%) (the entire shaded area in FIG. 14). The mass of adsorbate in the effluent during this period of MTZbreakthrough may be divided into two contributions: 1) the effluent massattributed to continued bleedthrough based on the initial bleedthroughconcentration at t=0, m_(efl, VB5-95%) (equal to about zero for a virginadsorbent bed), and 2) the remaining effluent mass, m_(efl, VM5-95%),that includes the mass attributed to the passage of the MTZ between 5and 95% breakthrough. The total mass of effluent for the period from t=0through t_(v95%) is m_(efl, V95%), equal to the sum ofm_(efl, V5%)+m_(efl, VB5-95%)+m_(efl, VM5-95%). An efficiency ofadsorption for the period from t=0 through t_(v95%), DAE_(V95%), is theratio of the cumulative amount adsorbed up until that time,m_(ads, V95%), and the total influent mass of adsorbate delivered to theadsorbent bed over that time period, m_(del, V95%) (e.g., DAE_(V95%) isthe ratio of m_(ads, V95%) over m_(del, V95%), equal to the ratio ofm_(ads, V95%) over m_(ads, V95%)+m_(efl, V95%)).

For a PPAV part that has undergone the prior steps of adsorption andpurge in the dynamic adsorption test, the effluent concentrationresponse resembles FIG. 15 , and similar mass balances, as applied forthe virgin PPAV part, may be applied to the cycled PPAV part, anddynamic adsorption efficiencies may be similarly derived. At t_(C5%),from a mass balance on the influent and effluent rates of adsorbate flowover time, the cumulative mass adsorbed by the bed is m_(ads, C5%) (aportion of the shaded area in FIG. 15 , between t=0 and t_(C5%)) and thecumulative mass of adsorbate in the effluent is m_(efl, C5%). Anefficiency of adsorption for that initial period, DAE_(C5%), is theratio of the amount adsorbed up until that time, m_(ads, C5%), and thetotal influent mass of adsorbate delivered to the adsorbent bed overthat time period (e.g., the ratio of m_(ads, C5%) overm_(efl, C5%)+m_(ads, C5%)) By time t_(C95%), with the passage of themajority of the MTZ into the bed effluent, the cumulative mass adsorbedby the bed is m_(ads, C95%) (the entire shaded area in FIG. 15 ). Themass of adsorbate in the effluent during this period of MTZ breakthroughmay be divided into two contributions: 1) the effluent mass attributedto continued bleedthrough based on the initial bleedthroughconcentration at t=0, m_(efl, CB5-95%) (which can be significantlymeasurable for a cycled adsorbent bed), and 2) the remaining effluentmass, m_(efl, CM5-95%), that includes the mass attributed to the passageof the MTZ between 5 and 95% breakthrough as defined by the initialbleedthrough as the breakthrough concentration baseline. The total massof effluent for the period from t=0 through t_(C95%) is m_(efl, C95%),equal to the sum of m_(efl, C5%)+m_(efl, CB5-95%)+m_(efl, CM5-95%). Anefficiency of adsorption for the period from t=0 through t_(C95%),DAE_(C95%), is the ratio of the cumulative amount adsorbed up until thattime, m_(ads, C95%), and the total influent mass of adsorbate deliveredto the adsorbent bed over that time period, m_(del, C95%) (e.g.,DAE_(C95%) is the ratio of m_(ads, C95%) over m_(del, C95%), equal tothe ratio of m_(ads, C95%) over m_(ads, C95%)±m_(efl, C95%)). Given thesignificantly measurable concentrations for the cycled PPAV part,bleedthrough may be compared between examples in terms of absolute massvalues (m_(efl, C5%)), and, as a measure of its contribution toadsorption inefficiency, in terms of mass values relative to totalbutane delivered (m_(del, C95%)), and relative to the total massadsorbed (m_(ads, C95%)).

In addition to analysis of the effluent data at 5% and 95% breakthroughfor the cycled PPAV for bleedthrough and efficiencies, analysis of theeffluent data was conducted at an intermediate breakthrough point of 25%of the influent 0.5 vol % butane, i.e., 0.125 vol % butane in theeffluent (See US 2020/0018265A1). FIG. 16 illustrates the derivation ofthe effluent mass values from the intermediate breakthrough of 0.125 vol% adsorbate in the effluent.

Determination of Pore Volumes and Surface Areas

Volume of pores (PV)<1.8 nm to 100 nm in size was measured by nitrogenadsorption porosimetry by the nitrogen gas adsorption method ISO15901-2:2006 using a Micromeritics ASAP 2420 (Norcross, Ga.). The samplepreparation procedure for nitrogen adsorption testing was to degas at250 C for at least two hours, typically to a stable <2 μg vacuum withthe sample isolated. The determination of pore volumes for pores <1.8 nmto 100 nm in size was from the desorption branch of the 77 K isothermfor a 0.1 g sample. The nitrogen adsorption isotherm data was analyzedby the Kelvin and Halsey equations to determine the distribution of porevolume with pore size of cylindrical pores according to the model ofBarrett, Joyner, and Halenda (“BJH”). The non-ideality factor was0.0000620. The density conversion factor was 0.0015468. The thermaltranspiration hard-sphere diameter was 3.860 Å. The molecularcross-sectional area was 0.162 nm2. The condensed layer thickness (Å)related to pore diameter (D, Å) used for the calculations was 0.4977[1n(D)]2-0.6981 ln(D)+2.5074. Target relative pressures for the isothermwere the following: 0.04, 0.05, 0.085, 0.125, 0.15, 0.18, 0.2, 0.355,0.5, 0.63, 0.77, 0.9, 0.95, 0.995, 0.95, 0.9, 0.8, 0.7, 0.6, 0.5, 0.45,0.4, 0.35, 0.3, 0.25, 0.2, 0.15, 0.12, 0.1, 0.07, 0.05, 0.03, 0.01.Actual points were recorded within an absolute or relative pressuretolerance of 5 mmHg or 5%, respectively, whichever was more stringent.Time between successive pressure readings during equilibration was 10seconds. Pore volumes are reported according to defined pore ranges,e.g., pore volume <1.8 nm (<18 Å) in size as PV_(<1.8 nm).

Determination of Incremental Adsorption Capacity

Micromeritics method. As known in the art, adsorption capacities may beequivalently measured by a number of means, including volumetric,gravimetric, and dynamic (flow) methods.

The “Micromeritics method” is a volumetric method based on a gas phasemass balance for the adsorbent sample-containing system of known volumeand temperature when exposed to changes in adsorbate gas phase pressure.For examples herein, a Micromeritics model ASAP 2020A expansion unit wasused (Micromeritics Instrument Corporation, Norcross, Ga. USA). By thismethod, as an initial state, adsorbate gas is contained in one vessel ofknown temperature, pressure, and volume, and adsorbate gas is containedin a second, adsorbent-containing vessel of known volume andtemperature, and a known different pressure. The two vessels are thenmade in fluid contact by the opening of a connecting valve. Afterequilibration to a final state (i.e., sufficient time for thermalequilibration and equilibrated adsorbate uptake by the adsorbent sample,as evidenced by a stabilized connected system pressure), the massbalance difference in gas phase adsorbate between the initial and finalstate is the mass change in adsorbed adsorbate by the adsorbent sample.Note in all examples reported herein, the adsorbate is n-butane.

The first step to determine IAC is sample preparation. Therepresentative adsorbent sample is oven-dried for more than 3 hours at110° C. The adsorbent sample shall include representative amounts of anyinert binders, fillers and structural components present in the nominalvolume of the adsorbent component when the Apparent Density valuedetermination equivalently includes the mass of the inert binders,fillers, and structural components in its mass numerator. Conversely,the adsorbent sample shall exclude these inert binders, fillers, andstructural components when the Apparent Density value equivalentlyexcludes the mass of the inert binders, fillers, and structuralcomponents in its numerator. The universal concept is to accuratelydefine the adsorptive properties for butane on a volume basis within thevolume.

A quartz sample tube is weighed with a rubber stopper and the weightrecorded (WO). About 0.1 g of adsorbent sample is loaded into the taredsample tube and the rubber stopper replaced. The rubber stopper isremoved, and the loaded sample tube is placed under a degassing portwhere the temperature is ramped to 250° C. at a rate of 10° C./min. Thesample is degassed at 250° C. for about 2 hours. The sample is allowedto cool and the tube is backfilled with nitrogen. The rubber stopper isreplaced and the degassed tube is weighed (W). Dry sample weight iscalculated as W−WO. The second step in the procedure is sample analysis.The water bath is set to 25±0.1° C. The instrument sample pressure isevacuated to less than 10 μmHg (usually less than 1 μmHg). Theinstrument plug and sample rubber stopper are removed, and the degassedtube is placed into the sample analysis port. The test is started. Theinstrument collects equilibrium butane isotherm data points around thefollowing absolute pressures (mmHg): 10, 20, 30, 40, 45, 150, 300, 350,400, 450, 600, 800, 600, 500, 450, 400, 350, 300, 150, 50, 45, 40, 35,30, 25). The mass adsorbed isotherm data point for 0.5 vol % at 1 atm(3.8 mmHg) reported herein was calculated from a power law regression(mass adsorbed=a Pressure^(b)) derived from a fit of the 10, 20, 30, and40 mmHg isotherm data points.

The IAC has been defined as the incremental adsorption capacity between5 and 50% n-butane at 25° C. A 5 vol % n-butane concentration (involume) at one atmosphere is provided by the equilibrium pressure insidethe sample tube of 38 mmHg. A 50 vol % n-butane concentration at oneatmosphere is provided by the equilibrium pressure inside the sampletube of 380 mmHg. Because equilibration at precisely 38 mmHg and 380mmHg may not be readily obtained, the mass of adsorbed n-butane per massof the adsorbent sample at 5 vol % n-butane concentration and at 50 vol% n-butane concentration is interpolated from a graph using the datapoints collected about the target 38 and 380 mmHg pressures. In theexamples provided herein, this was typically done using linearregression of the pressures between about 300 and about 450 mmHg and thepressures between about 30 and 45 mmHg on the desorption branch of theisotherm. Using the ideal gas law for n-butane and the adsorbentapparent density, the IAC can then be calculated as the capacity in g/gat 50 vol % n-butane minus the capacity at 5 vol % n-butane multipliedby the apparent density in g/L.

The McBain method is a gravimetric method. The adsorbent sample isoven-dried for more than 3 hours at 110° C. before loading onto a samplepan attached to a spring inside a sample tube. Then, the sample tube isinstalled into an apparatus as described. The adsorbent sample shallinclude representative amounts of any inert binders, fillers andstructural components present in the volume of the adsorbent componentwhen the Apparent Density value determination equivalently includes themass of the inert binders, fillers, and structural components in itsmass numerator. Conversely, the adsorbent sample shall exclude theseinert binders, fillers, and structural components when the ApparentDensity value equivalently excludes the mass of the inert binders,fillers, and structural components in its numerator. The universalconcept is to accurately define the adsorptive properties for butane ona volume basis within the volume.

A vacuum of less than 1 torr is applied to the sample tube, and theadsorbent sample is heated at 105° C. for 1 hour. The mass of theadsorbent sample is then determined by the extension amount of thespring using a cathetometer. After that, the sample tube is immersed ina temperature-controlled water bath at 25° C. Air was pumped out of thesample tube until the pressure inside the sample tube is 10⁻⁴ torr.n-Butane is introduced into the sample tube until equilibrium wasreached at a selected pressure. The tests are performed for two datasets of four selected equilibrium pressures each, taken about 38 torrand taken about 380 torr. The concentration of n-butane is based on theequilibrium pressure inside the sample tube. After each test at theselected equilibrium pressure, the mass of the adsorbent sample ismeasured based on the extension amount of the spring using cathetometer.The increased mass of the adsorbent sample is the amount of n-butaneadsorbed by the adsorbent sample. The mass of n-butane absorbed (ingram) per the mass of the adsorbent sample (in gram) is determined foreach test at different n-butane equilibrium pressures and plotted in agraph as a function of the concentration of n-butane (in % volume). A 5vol % n-butane concentration (in volume) at one atmosphere is providedby the equilibrium pressure inside the sample tube of 38 torr. A 50 vol% n-butane concentration at one atmosphere is provided by theequilibrium pressure inside the sample tube of 380 torr. Becauseequilibration at precisely 38 torr and 380 torr may not be readilyobtained, the mass of adsorbed n-butane per mass of the adsorbent sampleat 5 vol % n-butane concentration and at 50 vol % n-butane concentrationis interpolated from a graph using the data points collected about thetarget 38 and 380 torr pressures. The IAC is then calculated asdescribed herein.

Determination of Effective Volumetric Properties

The above methods are applicable for defining the nominal BWC, butaneactivity, IAC, and density properties of adsorbent. In contrast, theeffective volume of adsorbents takes into account the air gaps, voidsand other volumes sandwiched between the nominal volumes of adsorbentsalong the vapor flow path that lack adsorbent. For example, thosevolumes lacking adsorbent include, but are not limited to, the volumesbetween adsorbent volume 301 and 302 in FIG. 4 , the volume betweenadsorbent volume 204 and 301 in FIG. 4 that includes the port 108 andthe connecting conduit between canisters 101 and 300, and the volumebetween adsorbent volumes 202 and 203 in FIG. 4 that includes the plenumvolume 107. Thus, the effective volumetric properties of adsorbent referto the volume-averaged properties of the adsorbent volumes that takeinto account air gaps, voids and other volumes between the nominalvolumes of adsorbents that lack adsorbent along the vapor flow path.

The effective volume (V_(eff)) for a given length of the vapor flow pathis the sum of the nominal volumes of adsorbent (V_(nom, i)) presentalong that vapor path length plus adsorbent-free volumes along thatvapor flow path (V_(gap, j)).

V _(eff) =ΣV _(nom,i) +ΣV _(gap, j)

A volumetric adsorptive properties of an effective volume (B_(eff)),such as incremental adsorption capacity (g/L), apparent density (g/mL)and BWC (g/dL), is the sum of each property of the individual nominalvolumes to be considered as part of the effective volume (B_(nom, i))multiplied by each individual nominal volume (V_(nom, i)), then dividedby the total effective volume (V_(eff)):

B _(eff)=Σ(B _(nom,i) ×V _(nom,i))/V _(eff).

Thus, the term “effective incremental adsorption capacity” is the sum ofeach nominal incremental adsorption capacity multiplied by eachindividual nominal volume, and then divided by the total effectivevolume.

The term “effective butane working capacity (BWC)” is the sum of eachBWC value multiplied by each individual nominal volume, and then dividedby the total effective volume.

The term “effective apparent density” is the sum of each apparentdensity multiplied by each individual nominal volume, and then dividedby the total effective volume

The term “g-total BWC of the effective volume” is the sum of the g-totalBWC gram values of the nominal volumes within the effective volume.

In any of the aspects or embodiments, the description provides a PPAV asdescribed herein having an effective BWC (e.g., effective BWC less thanabout 10 g/dL or a value as described for BWC herein), effective IAC(e.g., effective IAC less than about 50 g/L or a value as described forIAC herein), effective apparent density, g-total BWC of the effectivevolume or a combination thereof, in an evaporative emission controlcanister system.

Determination of Honeycomb Dimensions and Cell Structure

FIG. 9 is an idealized generic illustration of a honeycomb cross-section600 for the purpose of showing key structure features, including theexternal edge or exterior surface 601, the parallel channels (or cellsin cross-section) 602, cell walls, 603, and the peripheral edge wall, or“skin”, 604. The channels have a width t_(c), cross sectional area A_(c)and perimeter length P_(c). The cells have a wall thickness t_(w) andthe skin has a thickness t_(s).

For determining dimensions of the cross-section, example honeycomb partswere cut to 1 mm thick slices with a diamond blade saw. The slice wasthen placed on a sheet of white printer paper with a ruler for scalereference and positioned level with the horizontal and vertical axeswithin the camera view finder, with the square grid of the cells in therotational orientation shown in FIG. 9 . The sheet of paper and sampleslice were placed on a 5000° K color corrected lamp lightbox, where aDSLR camera (Cannon EOS Rebel T3) was mounted above for photographing.The camera was approximately 7.5 inches above the lightbox and fittedwith a with a 50 mm fixed lens (1:1.8) and a 13 mm extension lens tube.With the slice backlit, multiple photographs were taken of thecross-sectional slice with alternative camera positions for obtaining aclear image. The images were analyzed by ImageJ, a public domain,Java-based image processing free software program developed at theNational Institutes of Health and the Laboratory for Optical andComputational Instrumentation. The pixels in the digital image werecalibrated, and line drawn across the face of the image provided thevarious measures of diameter, width, and thickness. Channel areas wereanalyzed by the “Analyze particles” command. Typically, image analysiswas measured on slices from one to five sample parts from the samepreparation lot as the part tested for DBL emissions, with the averagesof those dimensional analysis values reported in Tables 2-6.

FIGS. 10 and 11 illustrates the four 0°, 45°, 90°, and 135° rotationorientations applied for measuring outer diameter D_(o) and the innerdiameter D_(i) of the honeycomb 600. The outer diameters that were usedfor calculating the part volume, V, and then the g-total BWC from thepart volume, were measured by calipers on the same example part testedfor DBL emissions (D_(o, caliper)). The average value of the fourrotation measurements, D_(o, caliper), is provided in Tables 2-6. Thepart length, L, was also measured by calipers.

For the examples with high aspect ratio, slit-shaped cells, the PPAVparts were characterized by separate measurements of channel width andwall thickness according to the orientations of their component wide andnarrow channel widths. The x-axis refers to measurements made for thewide width directions, as oriented as a wide channel width in thedirection of the lines 901 and 903 in FIG. 12 for the crosshairanalysis, and the lines 911 and 911 in FIG. 13 for the n×n analysis (Seealso FIG. 46 ), with all channels elongated in this same horizontaldirection. The y-axis refers to measurements made for the narrow widthdirections, as oriented as a narrow channel height in the direction ofthe lines 902 and 904 in FIG. 12 for the crosshair analysis, and thelines 912 and 914 in FIG. 13 for the n×n crop analysis.

The skin thickness from inner and outer diameters, t_(s,D), in Tables2-6 was the difference between an image analysis outer diameter D_(o)and inner diameter D_(i), with both diameters the average values of thefour rotational measurements, i.e., the averages of D_(o,0°), D_(o,45°)D_(o,90°), D_(o,135°), and of D_(i,0°), D_(i,45°), D_(i,90°),D_(i,135°).

Using image analysis, the total channel cross sectional areas (A_(c))and perimeters (P_(c)) was obtained using the “Analyze particles”command. The average channel hydraulic diameter (t_(c,Dh)) wascalculated as 4ΣA_(c)/ΣP_(c).

FIGS. 12 and 13 illustrate the two constructions used by image analysisfor measuring cell wall thicknesses, from which an average wallthickness value, t_(w, avg), was then calculated and then also appliedfor the average cell pitch calculations. In one construction formeasuring wall thickness (FIG. 12 ), four crosshairs through about thecenter of the slice cross-section were drawn, two through the middle ofcells (lines 901 and 902) and two towards a base of the cells (lines 903and 904), with the ends of all four lines extending only as far asthrough the interior walls of the peripheral cells. The mid cell wallthickness, t_(w,m), and base cell wall thickness, t_(w,b), weredetermined as the average of the wall thickness through which mid-celllines 901 and 902 and base cell lines 903 and 904 traversed,respectively. For the illustrative example in FIG. 12 , each of thelines 901 through 904 traverse seven channels and eight cell walls. In asecond construction for measuring wall thickness (FIG. 13 ), a square“n×n” crop of cells was selected from the face of the cross-section,where the crop does not include any peripheral cells (i.e., thoselocated at the outer skin). Four mid-cell lines were drawn through themiddle of the peripheral cells of the crop, shown as lines 910 through913 in FIG. 13 , with the ends of all four lines extending only as faras through the corner channels of the peripheral cells. The wallthickness of the n×n crop, t_(w,n×n), was the average of the thicknessof all walls through which lines 910 through 913 traversed. For theillustrative example in FIG. 13 , each of the lines 910 through 913traverse five channels and four cell walls. For a given cross-sectionalslice subject to image analysis, the average wall thickness t_(w,avg) inTables 2-6 was calculated as the average of t_(w,m), t_(w,b), and,t_(w,n×n).

A channel width, t_(c,avg), was obtained from a plurality of channels inthe honeycomb cross-section that have approximately the samecross-sectional dimensions, which does not include partial cells at theperiphery. The channel width t_(c,avg) was calculated as the average ofthe channel widths t_(c,m), t_(c,b), and t_(c,n×n), as derived from themid- and base cell and n×n crop image analysis methods illustrated inFIGS. 12 and 13 . For example, the channel width t_(c,m) was the averagechannel width for cells traversed by the mid-cell lines 901 and 902 inFIG. 12 . The channel width t_(c,b) was the average channel width forcells traversed by the base-cell lines 903 and 904 in FIG. 12 . Thechannel width t_(c,n×n) determined using particle analysis byidentifying whole cells in the crop area yielding the area of each cell(void area). The average cell area was calculated and used to determinethe channel width using the square root of the area (i.e.,t_(c,n×n)=(A_(c,average)){circumflex over ( )}½).

One value of cell pitch, CP_(Dh), was calculated from the averagechannel hydraulic diameter of the whole honeycomb cross-sectional areathat includes all cells: the sum of t_(c, Dh) plus t_(w,avg). A secondcell pitch, CP_(tc), is based on the channel width of a plurality ofchannels that have approximately the same cross-sectional dimensions,which does not include the partial cells at the periphery. The cellpitch for a plurality of channels, CP_(tc), is the sum of t_(c,avg) plust_(w,avg).

The values for the ratio of external surface to solid volume, Sv, forthe honeycomb PPAV examples were calculated as the ratio of the totalchannel wall surface area (total channel periphery×caliper length), plusthe solid wall area at the two faces, divided by the caliper-determinedvolume corrected for the void fraction, ε, determined by image analysis,or [(ΣP_(c))+επD_(o, c) ²/4][(1−ε)V].

EXEMPLARY EMBODIMENTS

With reference to the accompanying Tables and Figures, the examples ofthe parallel passage adsorbent volume (PPAV) were activated carbonhoneycombs prepared with ceramic binder system and activated carbonpowder, similar to the ingredient types and process steps outlined inU.S. Pat. No. 5,914,294 (incorporated herein by reference in itsentirety), i.e., blending of ball clay, flux, organic extrusion aid,activated carbon, calcined kaolin, followed by extrusion, drying, andhigh temperature calcination. Comparative examples 1 and 12a werecommercially available NUCHAR® HCA honeycomb parts. Comparative example12b was commercially available NUCHAR® HCA-LBE honeycomb part(Ingevity®, North Charleston, S.C., USA). Examples 2 through 9 were madewith NUCHAR® RGC-PC acid-activated wood-based carbon powder (Ingevity®,North Charleston, S.C., USA), and had the following properties: Meanparticle size of 21.4 microns, d_(10%) of 3.8 microns, d_(50%) of 15.5microns, d_(90%) of 34.1 microns, powder butane activity (pBACT) of 44.8g/100 g, PV_(<1.8nm) of 0.185 cc/g, PV_(1.8-5nm) of 0.678 cc/g, andPV_(5-50nm) of 0.285 cc/g, and BET area of 1607 m²/g. Examples 10 and 11were made with Sabre Series® thermal-activated coconut-based carbonpowder (Carbon Resources, Oceanside, Calif., USA) and had the followingproperties: Mean particle size of 18.0 microns, d_(10%) of 3.6 microns,d_(50%) of 16.3 microns, d_(90%) of 39.4 microns, a powder butaneactivity (pBACT) of 29.4 g/100 g, PV_(<1.8nm) of 0.470 cc/g,PV_(1.8-5nm) of 0.114 cc/g, and PV_(5-50nm) of 0.025 cc/g, and a BETarea of 1226 m²/g.

In preparing example PPAV honeycombs, channel width, wall thickness, andcell pitch were varied by the size and spacing of the slots and pinsmachined into the extrusion die (e.g., see U.S. Pat. No. 6,080,348,incorporated herein by reference in its entirety). The majority of theexamples were extruded with dies that formed channels of squarecross-sectional shape, with two noted comparative examples with channelsof rectangular or “slit” cross-sectional shape. Proportions of blendingingredients were adjusted, especially the proportion of activatedcarbon, so that a similar range of BWC and IAC in the finished PPAVhoneycombs between inventive and comparative examples could be achievedin light of the varied void fractions in the finished parts resultingfrom the die selection. In some cases, an additional glass microspherepowder ingredient was added as a diluent for further tuning volumetricadsorptive capacity.

Table 2 provides the structural properties of the comparative andinventive examples of exemplary parallel passage adsorbent volumes inthe form of activated carbon honeycombs of about 35 mm in diameter and150 mm in length within a BWC range of 4.1-4.7 g/dL and IAC range of17-20 g/L. The Tables provide adsorptive property data for the examples,plus the worst day (day 2) diurnal breathing loss emission performancewhen these examples were configured as an adsorbent volume on thevent-side of a Type A evaporative emission control system. These examplePPAV honeycombs were cylindrically shaped with circular external crosssection of measured diameters equivalent to their hydraulic diameters(equal to area/periphery), though embodiments include PPAV honeycombs ofalternative external cross-sectional shapes of a cross-sectionaldimension to be characterized by a hydraulic diameter.

TABLE 2 Image Analysis, BWC, DBL (35 × 150 mm; 4.1-4.7 BWC). Example 1516 17 1 2 3 4 7 Comparative (C)/Inventive (I) C C C C I I I I Caliperlength (mm); L 150.2 151.3 150.6 150.2 151.2 150.9 150.5 151.2 Caliperdiameter (mm); D_(o,c) 35.0 35.3 35.3 34.7 34.9 34.4 34.8 35.0 L/D_(o,c)4.29 4.29 4.27 4.33 4.33 4.39 4.32 4.32 Volume (mL); V = π D_(o,c) ²L/4000 144.8 147.9 147.2 142.1 144.7 139.9 143.3 145.5 Total channelarea (mm²); ΣAc 598 572 419 566 529 538 432 218 Total channel periphery(mm); ΣP_(c) 648 1276 1316 1765 2314 2432 2584 2097 Outer diameter (mm);D_(o) 34.93 34.93 35.09 34.75 35.07 34.32 34.84 37.67 Skin thickness(mm) avg; t_(s,avg) 0.984 0.821 0.722 0.757 0.673 0.797 0.958 0.984 Wallthickness (mm) mid cell; t_(w,m) 0.836 0.386 0.615 0.299 0.280 0.2330.267 0.437 Wall thickness (mm) cell base; t_(w,b) 0.849 0.436 0.6360.313 0.283 0.234 0.270 0.442 Wall thickness (mm) nxn crop; t_(w,nxn)0.860 0.405 0.632 0.316 0.265 0.231 0.264 0.384 Wall thickness (mm) avg;t_(w,avg) 0.848 0.409 0.628 0.309 0.276 0.233 0.267 0.421 Pluralitychannel width (mm) avg; t_(c,avg) 4.195 1.876 1.364 1.326 0.940 0.9170.675 0.454 Average hydraulic diameter (mm); 4ΣA_(c)/ΣP_(c) 3.689 1.7921.275 1.283 0.914 0.885 0.669 0.415 Plurality width cell pitch (mm);CPt= t_(c, avg) + t_(w,avg) 5.043 2.285 1.992 1.635 1.216 1.150 0.9420.876 Hydraulic diameter cell pitch (mm); CP_(Dh) 4.537 2.201 1.9021.592 1.190 1.118 0.936 0.836 Void (%); ε = ΣA_(C)/(πD_(o) ²/4) 62.459.6 43.4 59.7 54.8 58.2 45.3 19.5 No. of cells; n_(c) 45 182 252 352627 666 986 1329 Cell density (cpsi); n_(c)/(πD_(o) ²/4) 30 123 168 239419 465 667 770 % whole cells (A_(c) > 0.85 avg A_(c)) 62.2 81.3 84.486.1 90.6 88.8 95.8 71.5 Surface/volume ratio, m²/m³; S_(v) 1.8 3.2 2.44.6 5.4 6.3 5.0 2.7 AD, g/ml 0.406 0.397 0.648 0.416 0.416 0.406 0.6190.560 BACT, g/100 g 12.80 12.84 8.47 11.69 12.61 12.47 8.44 9.40 BWC,g/dL 4.31 4.29 4.70 4.13 4.54 4.18 4.45 4.45 Retentivity, g/dL 0.89 0.810.79 0.73 0.70 0.88 0.78 0.82 BPR, % 82.9% 84.2% 85.6% 85.0% 86.6% 82.6%85.1% 84.4% g-Total BWC (g butane); PPAV BWC × V 6.24 6.35 6.92 5.876.57 5.85 6.38 6.48 Canister System Type A A A A A A A A GWC, g 144.9143.5 147.5 143.8 143.3 142.3 144.8 142.2 Purge, L 210 210 210.0 210 210210 210 210 BV purge 93.5 93.4 93.4 93.7 93.6 93.8 93.6 93.5 Day 2Emissions, mg 107.0 38.6 47.1 46.0 29.2 29.2 23.1 22.4

TABLE 3 Image Analysis, BWC, DBL - High dP Examples. Example 13 14 18 19Comparative (C)/Inventive (I) C C C C Caliper length (mm); L 151.0 152.0150.2 150.2 Caliper diameter (mm); D_(o, c) 35.0 35.4 34.7 34.7L/D_(o, c) 4.31 4.29 4.33 4.33 Volume (mL); V = π D_(o, c) ²L/4000 145.6150.0 142.1 142.1 Total channel area (mm²); ΣAc 148 189 566 566 Totalchannel periphery (mm); ΣP_(c) 886 1042 1765 1765 Outer diameter (mm);D_(o) 35.26 35.64 34.75 34.75 Skin thickness (mm) avg; t_(s, avg) 0.8940.705 0.757 0.757 Wall thickness (mm) mid cell; t_(w, m) 0.972 0.9030.299 0.299 Wall thickness (mm) cell base; t_(w, b) 0.956 0.866 0.3130.313 Wall thickness (mm) nxn crop; t_(w, nxn) 0.970 0.965 0.316 0.316Wall thickness (mm) avg; t_(w, avg) 0.966 0.911 0.309 0.309 Pluralitychannel width (mm) avg; t_(c, avg) 0.673 0.728 1.326 1.326 Averagechannel hydraulic diameter (mm); 4ΣA_(c)/ΣP_(c) 0.670 0.725 1.283 1.283Plurality width cell pitch (mm); CP_(tc) = t_(c, avg) + t_(w, avg) 1.6391.640 1.635 1.635 Hydraulic diameter cell pitch (mm); CP_(Dh) 1.6361.637 1.592 1.592 Void (%); ε = ΣA_(c)/(πD_(o) ²/4) 15.2 18.9 59.7 59.7No. of cells; n_(c) 345 364 352 352 Cell density (cpsi); n_(c)/(πD_(o)²/4) 228 235 239 239 % whole cells (A_(c) > 0.85 avg Ac) 70.7 89.3 86.186.1 Surface/volume ratio, m²/m³; S_(v) 1.1 1.3 4.6 4.6 AD, g/ml 0.7770.668 0.416 0.416 BACT, g/100 g 3.99 7.81 11.69 11.69 BWC, g/dL 2.784.43 4.13 4.13 Retentivity, g/dL 0.32 0.78 0.73 0.73 BPR, % 89.7% 85.0%85.0% 85.0% g-Total BWC (g butane); PPAV BWC × V 4.05 6.64 5.87 5.87Canister System Type A A A A GWC, g 140.8 143.7 140.8 143.3 Purge, L 210210 210 210 BV purge 93.5 93.3 93.7 93.7 Day 2 Emissions, mg 35.6 33.640.9 35.9

TABLE 4 Image Analysis, BWC, DBL, including slit-shaped cell examples.Example 24 25 22 23 Comparative (C)/Inventive (I) C-slit C-slit C ICaliper length (mm); L 151.5 151.4 150.5 150.7 Caliper diameter (mm);D_(o,c) 29.3 29.4 29.7 28.8 L/_(Do,c) 5.16 5.15 5.07 5.23 Volume (mL); V= πD_(o,c) ² L/4000 102.4 102.6 104.1 98.2 Total channel area (mm²); ΣAc390 380 405 362 Total channel periphery (mm); ΣP_(c) 1213 1247 1272 1619Outer diameter (mm); D_(o) 29.31 29.34 29.59 28.77 Skin thickness (mm)avg; t_(s,avg) 0.734 0.792 0.691 0.515 Wall thickness (mm) mid cell;t_(w,m) x-axis y-axis x-axis y-axis 0.301 0.259 0.268 0.378 0.342 0.398Wall thickness (mm) cell base; t_(w,b) 0.268 0.373 0.370 0.383 0.3090.271 Wall thickness (mm) nxn crop; t_(w,nxn) 0.226 0.256 0.206 0.2940.303 0.262 Wall thickness (mm) avg; t_(w,avg) 0.254 0.336 0.306 0.3580.304 0.264 Plurality channel width (mm) avg; t_(c,avg) 3.893 0.9182.722 0.922 1.353 0.916 Plurality width cell pitch (mm); CP_(tc) =t_(c,avg) + t_(w,avg) 4.147 1.254 3.080 1.228 1.658 1.180 Averagechannel hydraulic diameter (mm); 4ΣA_(c)/ΣP_(c) 1.288 1.218 1.275 0.894Hydraulic diameter cell pitch (mm); CP_(Dh) 1.583 1.550 1.580 1.158 Void(%); ε = ΣA_(c)/(πD_(o) ²/4) 57.9 56.2 59.0 55.7 No. of cells; n_(c) 161183 249 444 Cell density (cpsi); n_(c)/(πD_(o) ²/4) 151 174 234 441 %whole cells (A_(c) > 0.85 avg A_(c)) 55.8 66.7 85.0 88.5 Surface/volumeratio, m²/m³; S_(v) 4.3 4.2 4.5 5.6 AD, g/ml 0.265 0.265 0.366 0.439BACT, g/100 g 19.64 20.06 12.72 11.67 BWC, g/dL 4.30 4.30 4.04 4.28Retentivity, g/dL 0.90 1.02 0.61 0.85 BPR, % 82.7% 80.8% 86.9% 83.6%g-Total BWC (g butane); PPAV BWC x V 4.40 4.41 4.21 4.20 Canister SystemType A A A A GWC, g 141.4 138.2 142.2 142.5 Purge, L 210 210 210 210 BVpurge 95.4 95.3 95.3 95.5 Day 2 Emissions, mg 178.1 78.1 80.0 43.2

TABLE 5 Image Analysis for additional examples. Example 6 5 8 9 10 11Comparative (C)/Inventive (I) C I C I C I Caliper length (mm); L 150.0151.5 142.5 142.6 150.7 150.6 Caliper diameter (mm); D_(o,c) 35.0 35.042.2 42.3 36.0 34.4 L/D_(o,c) 4.29 4.33 3.38 3.37 4.19 4.37 Volume (mL);V = π D_(o,c) ² L/4000 144.3 145.5 199.4 200.2 153.4 140.2 Total channelarea (mm²); ΣAc 402 411 862 662 613 413 Total channel periphery (mm);ΣP_(c) 1220 2527 2657 3939 1899 2620 Outer diameter (mm); D_(o) 35.2735.20 42.01 42.40 35.80 34.03 Skin thickness (mm) avg; t_(s,avg) 1.0130.984 0.611 0.511 0.612 0.740 Wall thickness (mm) mid cell; t_(w,m)0.672 0.293 0.322 0.295 0.402 0.266 Wall thickness (mm) cell base;t_(w,b) 0.682 0.298 0.319 0.299 0.333 0.270 Wall thickness (mm) nxncrop; t_(w,nxn) 0.670 0.289 0.294 0.277 0.309 0.256 Wall thickness (mm)avg; t_(w,avg) 0.675 0.293 0.312 0.291 0.348 0.264 Plurality channelwidth (mm) avg; t_(c,avg) 1.381 0.667 1.365 0.688 1.367 0.647 Averagehydraulic diameter (mm); 4ΣA_(c)/ΣP_(c) 1.320 0.650 1.298 0.673 1.2920.630 Plurality width cell pitch (mm); CPt= t_(c, avg) + t_(w,avg) 2.0560.960 1.676 0.978 1.715 0.911 Hydraulic diameter cell pitch (mm);CP_(Dh) 1.995 0.943 1.610 0.963 1.640 0.894 Void (%); ε = ΣA_(C)/(πD_(o)²/4) 41.2 42.2 62.2 46.9 61.0 45.4 No. of cells; n_(c) 228 995 494 1465354 1033 Cell density (cpsi); n_(c)/(πD_(o) ²/4) 150 660 230 669 227 733% whole cells (A_(c) > 0.85 avg A_(c)) 90.4 90.0 87.7 92.4 84.9 93.4Surface/volume ratio, m²/m³; S_(v) 2.2 4.6 5.0 5.3 4.8 5.2 AD, g/ml0.564 0.525 0.251 0.411 0.329 0.661 BACT, g/100 g 13.16 12.66 12.81 7.8614.74 7.07 BWC, g/dL 5.92 5.47 2.95 2.98 3.01 2.86 Retentivity, g/dL1.50 1.18 0.26 0.25 1.83 1.81 BPR, % 79.8% 82.2% 91.8% 92.2% 62.2% 61.3%g-Total BWC (g butane); PPAV BWC × V 8.54 7.95 5.88 5.97 4.62 4.01Canister System Type A A A A A A GWC, g 149.5 145.1 140.7 142.8 142.3144.1 Purge, L 210 210 210 210 210 210 BV purge 93.6 93.5 91.3 91.3 93.293.7 Day 2 Emissions, mg 47.9 22.5 28.9 7.8 33.9 17.3

TABLE 6 Image Analysis, BWC, DBL—PPAV In-Series Examples. Example 9 12a12b 20a 20b 21a 21b Comparative (C)/Inventive (I) I C C I I C C Caliperlength (mm); L 142.6 100.1 99.4 99.0 101.0 100.0 99.9 Caliper diameter(mm); D_(o,c) 42.3 29.5 29.6 27.8 29.2 30.0 29.8 L/D_(o,c) 3.37 3.403.35 3.56 3.46 3.34 3.35 Volume (mL); V = π D_(o,c) ² L/4000 200.2 68.368.6 60.2 67.6 70.5 69.8 Total channel area (mm²); ΣAc 662 389 404 287319 406 404 Total channel periphery (mm); ΣP_(c) 3939 1226 1236 18171930 1291 1252 Outer diameter (mm); D_(o) 42.40 30.26 30.53 28.13 28.8429.65 29.52 Skin thickness (mm) avg; t_(s,avg) 0.511 0.897 1.028 0.4790.408 0.728 0.654 Wall thickness (mm) mid cell; t_(w,m) 0.295 0.3460.329 0.277 0.284 0.298 0.304 Wall thickness (mm) cell base; t_(w,b)0.299 0.356 0.334 0.279 0.285 0.301 0.318 Wall thickness (mm) nxn crop;t_(w,nxn) 0.277 0.345 0.293 0.261 0.270 0.294 0.311 Wall thickness (mm)avg; t_(w,avg) 0.291 0.349 0.319 0.272 0.280 0.297 0.311 Pluralitychannel width (mm) avg; t_(c,avg) 0.688 1.342 1.358 0.646 0.678 1.3381.369 Average hydraulic diameter (mm); 4ΣA_(c)/ΣP_(c) 0.673 1.269 1.3060.632 0.662 1.259 1.292 Plurality width cell pitch (mm); CPt=t_(c, avg) + t_(w,avg) 0.978 1.690 1.677 0.918 0.957 1.635 1.680Hydraulic diameter cell pitch (mm); CP_(Dh) 0.963 1.618 1.625 0.9040.941 1.557 1.603 Void (%); ε = ΣA_(C)/(πD_(o) ²/4) 46.9 54.2 55.1 46.248.9 58.9 59.1 No. of cells; n_(c) 1465 244 232 728 725 255 243 Celldensity (cpsi); n_(c)/(πD_(o) ²/4) 669 219 204 756 716 238 229 % wholecells (A_(c) > 0.85 avg A_(c)) 92.4 83.9 86.2 87.0 90.0 84.3 85.6Surface/volume ratio, m²/m³; S_(v) 5.3 3.9 4.0 5.9 5.7 4.7 4.6 AD, g/ml0.411 0.445 0.492 0.6537 0.4324 0.4068 0.5363 BACT, g/100 g 7.86 11.944.87 8.89 6.90 12.68 4.34 BWC, g/dL 2.98 4.34 2.26 4.71 2.77 4.34 2.18Retentivity, g/dL 0.25 0.98 0.14 1.10 0.21 0.82 0.15 BPR, % 92.2% 81.6%94.4% 81.0% 93.0% 84.2% 93.8% g-Total BWC (g butane); PPAV BWC × V 5.972.96 1.55 2.84 1.87 3.06 1.52 Canister System Type B B C C Load dP ofsystem at 40 lpm, kPa 1.19 1.59 1.43 1.00 Purge dP of system at 40 lpm,kPa 1.90 2.45 1.66 1.27 GWC, g 122.2 121.8 143.7 144.9 Purge, L 210 210210.8 210.8 BV purge 91.3 93.9 80.8 80.4 Day 2 Emissions, mg 9.4 12.44.4 9.4

As can be seen in the data in Tables 2-6, the evaporative emissioncontrol systems of the present disclosure have substantially reduced DBLemissions with use of the inventive examples of parallel passageadsorbent in a vent-side volume versus the use of the comparativeexamples. The examples in Table 2, in the form of activated carbon PPAVhoneycombs of approximately 35 mm diameter and 150 mm length, weretested in the vent-side auxiliary canister 300 in a type A canistersystem, as described above and in Table 1. FIG. 17 shows comparativeexample carbon honeycombs with average channel hydraulic diameters of1.25 mm or greater having day 2 DBL emissions of greater than 39 mg(open symbols, ◯), and appearing to level off between 1.8 and 1.25 mmhydraulic diameter. In contrast, the inventive examples with narrowerchannels of 0.4-0.9 mm channel hydraulic diameter have substantiallylower emissions, at less than 30 mg day 2 emissions (closed symbols, ●).FIG. 18 shows that the lower emissions for the inventive examplescorrelate with lower cell pitch of 0.8-1.2 mm based on the hydraulicdiameter, especially compared with 1.6-2.2 mm cell pitch for thecomparative examples where the high emissions appeared to have leveledoff as a function of pitch.

Likewise, as shown in FIG. 19 , the lower emissions of the inventiveexamples also correlate with the plurality of their channel widths ofabout 0.4-0.9 mm being much smaller than those of the comparativeexamples at greater than 1.3 mm width, and for their cell pitch based onthe plurality of channel widths also smaller at 0.9-1.2 mm, comparedwith about 1.6-2 mm for the comparative examples where the higheremissions appeared to have leveled off as a function of pitch (FIG. 20). An alternative way to show the effect is according to cell density,where emissions appeared to level off between about 125 and 240 cpsi forthe comparative examples, but were substantially lower for the highercell density, inventive examples (FIG. 21 ).

Surprisingly, as shown in FIG. 22 , the benefit to canister systememissions by the use of the inventive examples over the comparativeexamples was not a result of lower wall thickness. For example,comparative examples 1 and 17 had the same 46-47 mg emissions despitemore than a twofold difference in cell wall thickness. Likewise, despitefalling within the same 0.27-0.42 mm range of wall thickness,comparative examples 1 and 16 had substantially higher emissions thaninventive examples 2, 4 and 7.

It should be stressed that there was no trend or correlation of the DBLemissions of the inventive examples with macropore distribution andmacropore volume properties. With reference to Tables 7-11, themacropore distribution values of M/M and M/m, as well as PV pore volumesfor pores 0.05-100 micron size and particle density were determined inaccordance with ISO 15901-1 (2016) as described in U.S. Pat. No.9,322,368 and in U.S. Pat. No. 9,174,195, respectively, which areincorporated herein by reference in their entirety. The '368 patent and'195 patent teach that emission control performance is optimal when inthe ranges of 30-70% M/M and 65-150% M/m. For example, as shown in FIG.23 , the values of the variety of PPAV parts in Tables 7-11 for bothcomparative and inventive parts were in the same ranges, therefore, nota factor in the differentiated performance of the inventive examples,akin to the similarities in ingredients, BWC, external dimensions, andIAC. In fact, the M/M and M/m values were often outside of the taughtoptimal ranges for both example groups. In terms of pore volumes on avolume of cell wall basis (multiplying the cc/g pore volume by themeasured particle density (g/cc) of the example parts so as to normalizefor differences potentially resulting from differences in extrusionformulations), FIG. 24 shows no differences between the comparative andinventive example groups for the volumes of macropores of both smallsize (0.05-1 μm) and of large size (1-100 μm). About 20% of the wallvolume (0.2 cc/cc-wall) is small size macropores, and less than 5% ofthe wall volume (<0.05 cc/cc-wall) is large size macropores. (Note thatExample 7 is an outlier with a high volume of macropores, particularlyof smaller size, due to the ingredient formulation used in itspreparation for tuning its volumetric adsorptive properties into thecomparable range as the other example groupings in Table 7).

TABLE 7 dP, IAC, PV (35 × 150 mm; 4.1-4.7 BWC). Example 15 16 17 1 2 3 47 Comparative (C)/Inventive (I) C C C C I I I I Caliper length (mm); L150.2 151.3 150.6 150.2 151.2 150.9 150.5 151.2 Caliper diameter (mm);D_(o,c) 35.0 35.3 35.3 34.7 34.9 34.4 34.8 35.0 Wall thickness (mm) avg;t_(w,avg) 0.848 0.409 0.628 0.309 0.276 0.233 0.267 0.421 Averagechannel hydraulic diameter (mm); 3.689 1.792 1.275 1.283 0.914 0.8850.669 0.415 4ΣA_(c)/ΣP_(c) Hydraulic diameter cell pitch (mm); CP_(Dh)4.537 2.201 1.902 1.592 1.190 1.118 0.936 0.836 Plurality width cellpitch (mm); CP_(tc) = t_(c, avg) + 5.043 2.285 1.992 1.635 1.216 1.1500.942 0.876 t_(w, avg) Cell density (cpsi); n_(c)/(πD_(o) ²/4) 30 123168 239 419 465 667 770 dP o at 40 lpm, kPa 0.034 0.050 0.000 0.0620.110 0.151 0.295 0.829 dP at 46 cm/s, kPa 0.027 0.036 0.000 0.058 0.1050.127 0.291 0.805 IAC, g/L 18.5 18.9 20.3 17.1 19.5 16.7 19.4 17.8 5%butane capacity (g/g); m_(5%) 0.065 0.066 0.044 0.067 0.068 0.067 0.0440.050 50% butane capacity (g/g); m_(5%) 0.111 0.114 0.076 0.108 0.1150.108 0.075 0.081 Ratio m_(0.5%)/m_(50%) 0.324 0.331 0.325 0.348 0.3310.357 0.326 0.348 Ratio m_(5%)/m_(50%) 0.588 0.583 0.586 0.620 0.5900.619 0.585 0.611 Particle density < 100 μm, g/cc 0.982 0.968 1.1671.008 0.987 1.016 1.186 0.752 BET Area, m²/g 406 415 288 412 443 410 288307 PV_(<1.8 nm,) cc/g 0.046 0.047 0.037 0.054 0.062 0.059 0.041 0.041PV_(1.8-5 nm,) cc/g 0.182 0.186 0.113 0.154 0.168 0.160 0.108 0.129PV_(5-50 nm,) cc/g 0.090 0.089 0.081 0.118 0.118 0.071 0.072 0.057PV_(<0.1 μm,) cc/g 0.327 0.328 0.245 0.335 0.362 0.293 0.230 0.230PV_(0.1-100 μm,) cc/g 0.208 0.209 0.136 0.226 0.169 0.216 0.127 0.443PV_(0.05-1 μm,) cc/g 0.224 0.219 0.198 0.221 0.217 0.212 0.198 0.419PV_(1-100 μm,) cc/g 0.012 0.016 0.011 0.031 0.024 0.028 0.012 0.042PV_(0.05-0.5 μm,) cc/g 0.223 0.218 0.198 0.217 0.215 0.212 0.197 0.168PV_(0.05-100 μm,) cc/g 0.236 0.235 0.209 0.252 0.241 0.240 0.210 0.461PV_(0.05-1 μm)/PV_(0.05-100 μm,) % 94.9% 93.2% 94.8% 87.6% 90.0% 88.4%94.2% 90.8% PV_(0.05-0.5 μm)/PV_(0.05-100 μm,) “M/M” 94.5% 92.6% 94.6%86.3% 89.0% 88.4% 93.9% 36.5% PV_(0.1-100 μm)/PV_(<0.1 μm,) “M/M” 63.5%63.7% 55.4% 67.5% 46.7% 73.6% 55.3%  192% PV_(0.05-1 μm), cc/cc-wall0.220 0.212 0.231 0.223 0.214 0.216 0.234 0.315 PV_(1-100 μm),cc/cc-wall 0.012 0.015 0.013 0.031 0.024 0.028 0.014 0.032

TABLE 8 dP, IAC, PV - High dP Examples. Example 13 14 18 19 Comparative(C)/Inventive (I) C C C C Caliper length (mm); L 151.0   152.0   150.2150.2 Caliper diameter (mm); D_(o, c) 35.0   35.4   34.7 34.7 Wallthickness (mm) avg; t_(w, avg) 0.966 0.911 0.309 0.309 Average channelhydraulic diameter (mm); 0.670 0.725 1.283 1.283 4ΣA_(c)/ΣP_(c)Hydraulic diameter cell pitch (mm); CP_(Dh) 1.636 1.637 1.592 1.592Plurality width cell pitch(mm); CP_(tc) = t_(c, avg) + t_(w, avg) 1.6391.640 1.635 1.635 Cell density (cpsi); nc/(πDo 2/4) 228     235     239239 dP only at 40 lpm, kPa 0.563 0.599 0.421 0.406 dP at 46 cm/s, kPa0.541 0.556 0.287 0.287 IAC, g/L 12.4   20.4   17.1 17.1 5% butanecapacity (g/g); m5% 0.021 0.041 0.067 0.067 50% butane capacity (g/g);m50% 0.037 0.072 0.108 0.108 Ratio m0.5%/m50% 0.303 0.308 0.348 0.348Ratio m5%/m50% 0.574 0.574 0.620 0.620 Particle density <100 μm, cc/g0.897 0.805 1.008 1.008 BET Area, m²/g 138     326     412 412PV_(<1.8 nm), cc/g 0.013 0.039 0.054 0.054 PV_(1.8-5 nm), cc/g 0.0640.141 0.154 0.154 PV_(5-50 nm), cc/g 0.037 0.078 0.118 0.118PV_(<0.1 μm), cc/g 0.117 0.262 0.335 0.335 PV_(0.1-100 μm), cc/g 0.3560.390 0.226 0.226 PV_(0.05-1 mm), cc/g 0.376 0.410 0.221 0.221PV_(1-100 mm), cc/g 0.026 0.020 0.031 0.031 PV_(0.05-0.5 μm), cc/g 0.2600.245 0.217 0.217 PV_(0.05-100 μm), cc/g 0.402 0.431 0.252 0.252PV_(0.05-1 μm)/PV_(0.05-100 μm), % 93.5% 95.3% 87.6% 87.6%PV_(0.05-0.5 μm)/PV_(0.05-100 μm), “M/M” 64.6% 56.8% 86.3% 86.3%PV_(0.1-100 μm)/PV_(<0.1 μm), “M/m”  304%  149% 67.5% 67.5%PV_(0.05-1 μm), cc/cc-wall 0.419 0.510 0.219 0.219 PV_(1-100 μm),cc/cc-wall 0.029 0.025 0.031 0.031

TABLE 9 dP, IAC, PV, including slit-shaped cell examples. Example 24 2522 23 Comparative (C)/Inventive (I) C-slit C-slit C I Caliper length(mm); L 151.5 151.4 150.5 150.7 Caliper diameter (mm); D_(o,c) 29.3 29.429.7 28.8 Wall thickness (mm) avg; t_(w,avg) x-axis y-axis x-axis y-axis0.304 0.264 0.254 0.336 0.306 0.358 Average channel hydraulic diameter(mm); 4ΣA_(c)/ΣP_(c) 1.288 1.218 1.275 0.894 Hydraulic diameter cellpitch (mm); CP_(Dh) 1.583 1.550 1.580 1.158 Plurality width cellpitch(mm); CP_(tc) = t_(c, avg) + t_(w, avg) 4.147 1.254 3.080 1.2281.658 1.180 Cell density (cpsi); n_(c)/(πD_(o) ²/4) 151 174 234 441 dPonly at 40 lpm, kPa 0.087 0.189 0.308 0.147 dP at 46 cm/s, kPa 0.0770.176 0.219 0.120 IAC, g/L 18.3 17.0 17.3 17.3 5% butane capacity (g/g);m5% 0.106 0.103 0.068 0.061 50% butane capacity (g/g); m50% 0.175 0.1670.115 0.100 Ratio m0.5%/m50% 0.349 0.346 0.334 0.343 Ratio m5%/m50%0.606 0.615 0.590 0.606 Particle density <100 μm, g/cc 0.841 0.800 0.9481.002 BET Area, m²/g 701 622 418 363 PV_(<1.8 nm), cc/g 0.095 0.0800.057 0.045 PV_(1.8-5 nm), cc/g 0.290 0.264 0.160 0.155 PV_(5-50 nm),cc/g 0.172 0.158 0.120 0.101 PV_(<0.1 μm), cc/g 0.570 0.513 0.348 0.311PV_(0.1-100 μm), cc/g 0.373 0.352 0.204 0.215 PV_(0.05-1 μm), cc/g 0.3230.320 0.207 0.214 PV_(1-100 μm), cc/g 0.072 0.050 0.033 0.032PV_(0.05-0.5 μm), cc/g 0.312 0.312 0.205 0.212 PV_(0.05-100 μm), cc/g0.395 0.370 0.240 0.246 PV_(0.05-1 μm)/PV_(0.05-100 μm), % 81.8% 86.6%86.4% 87.1% PV_(0.05-0.5 μm)/PV_(0.05-100 μm), “M/M” 79.1% 84.3% 85.4%86.2% PV_(0.1-100 μm)/PV_(<0.1 μm), “M/m” 65.4% 68.6% 58.5% 69.2%PV_(0.05-1 μm), cc/cc-wall 0.272 0.256 0.196 0.214 PV_(1-100 μm),cc/cc-wall 0.061 0.040 0.031 0.032

TABLE 10 dP, IAC, PV—alternative BWC, carbon and dimension examples.Example 6 5 8 9 10 11 Comparative (C)/Inventive (I) C I C I C I Caliperlength (mm); L 150.0 151.5 142.5 142.6 150.7 150.6 Caliper diameter(mm); D_(o,c) 35.0 35.0 42.2 42.3 36.0 34.4 Wall thickness (mm) avg;t_(w,avg) 0.675 0.293 0.312 0.291 0.348 0.264 Average channel hydraulicdiameter (mm); 4ΣA_(c)/ΣP_(c) 1.320 0.650 1.298 0.673 1.292 0.630Hydraulic diameter cell pitch (mm); CP_(Dh) 1.995 0.943 1.610 0.9631.640 0.894 Plurality width cell pitch (mm); CP_(tc) = t_(c, avg) +t_(w, avg) 2.056 0.960 1.676 0.978 1.715 0.911 Cell density (cpsi);n_(c)/(πD_(o) ²/4) 150 660 230 669 227 733 dP o at 40 lpm, kPa 0.0740.281 0.035 0.249 0.054 0.264 dP at 46 cm/s, kPa 0.065 0.261 0.034 0.2470.054 0.250 IAC, g/L 26.3 24.6 10.4 10.4 9.9 10.0 5% butane capacity(g/g); m_(5%) 0.068 0.069 0.068 0.040 0.121 0.054 50% butane capacity(g/g); m_(5%) 0.115 0.115 0.109 0.065 0.151 0.070 Ratio m_(0.5%)/m_(50%)0.331 0.332 0.359 0.338 0.577 0.559 Ratio m_(5%)/m_(50%) 0.593 0.5940.621 0.610 0.801 0.783 Particle density < 100 μm, g/cc 1.304 1.0240.745 0.972 0.896 1.543 BET Area, m²/g 433 444 407 250 588 276PV_(<1.8 nm,) cc/g 0.059 0.058 0.056 0.031 0.225 0.099 PV_(1.8-5 nm,)cc/g 0.167 0.173 0.169 0.108 0.053 0.035 PV_(5-50 nm,) cc/g 0.101 0.1120.075 0.048 0.017 0.009 PV_(<0.1 μm,) cc/g 0.337 0.362 0.305 0.191 0.3030.145 PV_(0.1-100 μm,) cc/g 0.163 0.156 0.454 0.406 0.351 0.230PV_(0.05-1 μm,) cc/g 0.220 0.206 0.427 0.407 0.331 0.215 PV_(1-100 μm,)cc/g 0.012 0.021 0.049 0.032 0.032 0.022 PV_(0.05-0.5 μm,) cc/g 0.2190.205 0.189 0.200 0.250 0.148 PV_(0.05-100 μm,) cc/g 0.233 0.227 0.4760.438 0.363 0.237 PV_(0.05-1 μm)/PV_(0.05-100 μm,) % 94.6% 90.9% 89.7%92.8% 91.2% 90.6% PV_(0.05-0.5 μm)/PV_(0.05-100 μm,) “M/M” 94.0% 90.3%39.7% 45.7% 68.9% 62.5% PV_(0.1-100 μm)/PV_(<0.1 μm,) “M/M” 48.3% 42.9% 149%  212%  116%  158% PV_(0.05-1 μm), cc/cc-wall 0.287 0.211 0.3180.396 0.297 0.332 PV_(1-100 μm), cc/cc-wall 0.016 0.022 0.037 0.0310.029 0.034

TABLE 11 dP, IAC, PV—PPAV In-Series Examples. Example 9 12a 12b 20a 20b21a 21b Comparative (C)/Inventive (I) I C C I I C C Caliper length (mm);L 142.6 100.1 99.4 99.0 101.0 100.0 99.9 Caliper diameter (mm); D_(o,c)42.3 29.5 29.6 27.8 29.2 30.0 29.8 Wall thickness (mm) avg; t_(w,avg)0.291 0.349 0.319 0.272 0.280 0.297 0.311 Average channel hydraulicdiameter (mm); 4ΣA_(c)/ΣP_(c) 0.673 1.269 1.306 0.632 0.662 1.259 1.292Hydraulic diameter cell pitch (mm); CP_(Dh) 0.963 1.618 1.625 0.9040.941 1.557 1.603 Plurality width cell pitch (mm); CP_(tc) =t_(c, avg) + t_(w, avg) 0.978 1.690 1.677 0.918 0.957 1.635 1.680 Celldensity (cpsi); n_(c)/(πD_(o) ²/4) 669 219 204 756 716 238 229 dP o at40 lpm, kPa 0.249 0.140 0.000 0.000 0.000 0.000 0.000 dP at 46 cm/s, kPa0.247 0.112 0.000 0.000 0.000 0.000 0.000 IAC, g/L 10.4 20.8 7.8 10.410.4 19.0 9.4 5% butane capacity (g/g); m_(5%) 0.040 0.069 0.023 0.0480.036 0.064 0.022 50% butane capacity (g/g); m_(5%) 0.065 0.115 0.0380.079 0.060 0.111 0.040 Ratio m_(0.5%)/m_(50%) 0.338 0.336 0.312 0.3580.329 0.317 0.278 Ratio m_(5%)/m_(50%) 0.610 0.595 0.586 0.605 0.5990.578 0.561 Particle density < 100 μm, g/cc 0.972 1.051 1.317 1.2590.831 0.961 1.290 BET Area, m²/g 250 415 153 295 220 409 136PV_(<1.8 nm,) cc/g 0.031 0.057 0.016 0.043 0.027 0.043 0.010PV_(1.8-5 nm,) cc/g 0.108 0.159 0.063 0.119 0.095 0.183 0.060PV_(5-50 nm,) cc/g 0.048 0.121 0.069 0.054 0.044 0.100 0.070PV_(<0.1 μm,) cc/g 0.191 0.347 0.168 0.220 0.170 0.334 0.157PV_(0.1-100 μm,) cc/g 0.406 0.194 0.128 0.177 0.431 0.224 0.145PV_(0.05-1 μm,) cc/g 0.407 0.210 0.197 0.177 0.421 0.223 0.201PV_(1-100 μm,) cc/g 0.032 0.015 0.011 0.011 0.044 0.027 0.017PV_(0.05-0.5 μm,) cc/g 0.200 0.208 0.197 0.175 0.211 0.219 0.200PV_(0.05-100 μm,) cc/g 0.438 0.225 0.208 0.188 0.465 0.250 0.219PV_(0.05-1 μm)/PV_(0.05-100 μm,) % 92.8% 93.2% 94.8% 94.2% 90.6% 89.2%92.1% PV_(0.05-0.5 μm)/PV_(0.05-100 μm,) “M/M” 45.7% 92.7% 94.9% 92.8%45.4% 87.8% 91.4% PV_(0.1-100 μm)/PV_(<0.1 μm,) “M/M”  212% 55.8% 76.3%80.5% 254% 67.0% 92.1% PV_(0.05-1 μm), cc/cc-wall 0.396 0.221 0.2590.223 0.350 0.214 0.259 PV_(1-100 μm), cc/cc-wall 0.031 0.016 0.0140.014 0.037 0.026 0.022

In seeking a cause for the lower emissions by the inventive examples,the effect of flow restriction by the PPAV part in the auxiliarycanister was considered and was found to only partially account for thefull improvement. In one set of experiments, flow restriction of Example1 was increased by placing an orifice plate “before” the Example 1 PPAVpart (location “B” in FIG. 5 ) as comparative Example 18, or by placingan orifice plate “after” the Example 1 PPAV part (location “A” in FIG. 5) as comparative Example 19. Examples 18 and 19 were tested in the sameway as Example 1 in Table 7 and the DBL emissions were measured. Asshown in FIG. 25 , there was some benefit of the added flow restrictionfor the orifice plates present in Examples 18 and 19 compared with theorifice plate-free Example 1, but the high cell density, low cell pitchinventive Examples 2-4 and 7 of otherwise equivalent size and adsorptiveproperties as Example 1 exhibited consistently lower emissions, meaningtheir benefit exceeds any small benefit that might be attributable toflow restriction effects. In another experiment of the flow restrictioneffect, a PPAV of similar 1.6 mm cell pitch size as Example 1 wasprepared (Example 14), but with smaller parallel passage channels andthicker cell walls by use of an alternative extrusion die and withmodifications in the formulation so that the net volumetric adsorptiveproperties would be about the same as Example 1 and the other examplesof Table 2. The result of the thick wall extrusion was an example withhigh flow restriction at the 1.6 mm cell pitch of the comparativeexamples, but with the channel width of the size of inventive examples.As shown in FIG. 25 , the bleed emissions of the thick cell wall Example14 follow the trend of somewhat lower emissions from Examples 18 and 19,thereby allowing attribution of the lower emissions to its higher flowrestriction properties (and notably with the lower emissions of Example14 over Example 1 despite its near fourfold greater cell wallthickness). In addition, the bleed emissions of Example 14, despite itsnarrow channel width, did not have as low emissions as the inventiveexamples of similar channel width but of low pitch, reinforcing thespecial significance of low cell pitch and high cell density onemissions performance by the inventive examples (see FIG. 26 ).

Additional tests revealed the unexpected significance of low pitch andsmall hydraulic diameter of the channels for low emissions over PPAVparts of only a partial plurality of low cell pitch and only a partialplurality of narrow channel width as provided by channels of high aspectratio shape, e.g., slit-shaped channels. A special die was used forpreparing Examples 24 and 25 with 4:1 and 3:1 ratio slit-shapedchannels, respectively (rectangular shaped cells with long sides fourtimes or three times the length of short sides), where the short channelsides were of about 1 mm length (see Tables 4 and 9). These slit-shapedchannel parts were in the form of 29 mm diameter by 150 mm lengthmonoliths with a BWC of about 4.3 g/dL. (Note: the wall thickness valueused to determine hydraulic diameter cell pitch was the average of the xand y wall thickness.) While the overall cell densities of 166-179 cpsiand hydraulic diameter-based cell pitch and channel width propertieswere similar to other comparative examples, the cell pitch perpendicularto the short direction, at 1.2-1.5 mm, was much shorter than comparativeexamples. Similar size and BWC parts with square shaped channel of 234and 441 cpsi cell densities (Examples 22 and 23, respectively) were alsoprepared and tested in canister systems (FIG. 27 ). The canister systemdata show unexpectedly high emissions by the slit-shaped channelExamples 24 and 25 compared with both the square-shaped channel Examples22 and 23, with the emissions trends for the slit-shaped Examples 24 and25 following their average width-based cell pitch or hydraulic diametercell pitch properties as opposed to, and despite, their narrow channelproperties (see FIGS. 28 and 29 ).

For examples with conventional 1.6 mm cell pitch compared with examplesof lower cell pitch but with otherwise equivalent external size andadsorptive properties (BWC, IAC), there is a consistent trend of loweremissions in the same Type A canister system by the low pitch examplesacross a wide range of adsorptive properties. FIGS. 30 and 31 show thelower emissions across a wide range of BWC and IAC, respectively. Thecomparative example data point at 1.6 mm cell in these two figures haveotherwise equivalent examples at lower cell pitch, include the following(Examples of Tables 2 and 3). Comparative Example 8 and inventiveExample 9 were prepared with similar dimensions of about 42 mm diameterand 142 mm length, similar cell wall thickness of about 0.3 mm, similarBWC of about 3 g/dL, and similar IAC of about 10 g/L; however, owing tothe lower cell pitch (about 1 mm based on plurality channel width oraverage channel hydraulic diameter, compared with about 1.6-1.7 mm) andsmaller channel opening (about 0.7 mm based on plurality channel widthor average channel hydraulic diameter, compared with about 1.3-1.4 mm),Example 9 as the adsorbent volume fill in the auxiliary canister in atype A canister had 8 mg DBL day 2 emissions, which was 73% loweremissions compared with the emission of about 29 mg with Example 8 asthe auxiliary canister adsorbent volume fill. Comparative Example 10 andinventive Example 11 were prepared with highly microporous coconut-basedcarbon powder instead of mesoporous wood-based carbon powder, with theresulting PPAV honeycomb having similar dimensions of about 35 mmdiameter and 150 mm length, similar BWC of about 3 g/dL, and similar IACof about 10 g/L; however, owing to the lower pitch (about 0.9 mm forplurality channel width or average channel hydraulic diameter, comparedwith about 1.6-1.7 mm) and smaller channel pitch (about 0.6 mm based onplurality channel width or average channel hydraulic diameter, comparedwith about 1.3-1.4 mm), Example 11 as the adsorbent volume fill in theauxiliary canister in a type A canister system had about 17 mg DBL day 2emissions, which was about half the 34 mg emissions produced withExample 10 as the auxiliary canister adsorbent volume fill. ComparativeExamples 1 and 6 versus inventive Examples 2-5 and 7 were of 35 mm×150mm length, with 4.2-5.9 g/dL BWC and 17-26 g/L IAC (Tables 2 and 3) andhave similar cell pitch, channel width, and emissions comparisons andcontrasts as the Examples 8-11, above.

The embodiments of lower cell pitch and smaller channel width wereleveraged in examples. Unexpectedly, the PPAVs as described hereindemonstrated greater canister simplicity, lower flow restriction, andlower DBL emissions. For example, comparative examples 12a and 12b wereobtained as commercially available PPAV honeycomb NUCHAR® HCA andHCA-LBE parts of approximately 29 mm diameter and 100 mm length withconventional 1.6-1.7 mm cell pitch and 1.2-1.3 mm channel width, andwere tested in combination as in-series pair within a type B canistersystem (example 12a+bB) in order to attain <20 mg DBL day 2 emissions(12.4 mg). Canister systems are configured in some vehicle platformswith multiple PPAV honeycombs in-series in this way for meetingemissions requirements, with a one part having a BWC of about 4-4.5 g/dLin-series with another part having a BWC of <3 g/dL located closest tothe system vent, as especially needed when only low volumes of purge areavailable with advanced engine technologies, e.g., hybrid vehicles, GDIengines, start/stop and turbo-assisted engines. By comparison, in theauxiliary canister of the type B canister system, inventive Example 9Bwith a single PPAV honeycomb, of much smaller pitch of about 1 mm andsmaller channel width and hydraulic diameter of less than 0.7 mm thaneither Example 12a or 12b, had 9 mg emissions, 24% lower than the pairedconventional PPAV honeycomb Example 12a+bB. Significantly, while bothexamples 9B and 12a+bB had DBL day 2 emissions of <20 mg, the example 9Benabled a canister system B to have substantially lower emissions with asingle PPAV honeycomb in place for added simplicity of design, and toadditionally have a system load flow restriction at 40 slpm (1.18 kPa)that was 25% less than that of example 12a+bB and a system purge flowrestriction at 40 slpm (1.90 kPa) that was 22% less than that of example12a+bB, allowing more flexibility in the canister system design choicesthat affect flow restriction (e.g., screens, filters, valves, conduits,etc).

Embodiments were also tested in canister systems challenged with a widerange of purge volumes, demonstrating the consistent benefit overcomparative examples from low cell pitch and low channel width as theamount of purge was reduced. FIGS. 32 and 33 show the consistently lowerday 2 DBL emissions by inventive Example 4 over comparative Example 1when placed in the 2.1 L LEV II Type A canister system as the PPAV partand tested over a range of 210-310 L and 94-138 BV (also, see Table 12).

TABLE 12 Effect of Purge - LEV II System. Example: 1 4 Comparative(C)/Inventive (I): Comparative Inventive Canister System Type: A A Day 2Day 2 Purge, Liters BV Emissions, mg BV Emissions, mg 310 138.3 13.9138.2 7.8 256 114.2 20.5 114.1 10.2 210 93.7 46.0 93.6 23.1

Another set of experiments on the effects of purge volume on DBLemissions performance were conducted with a commercial LEV III canistersystem with the adsorbent volumes configured as shown in FIG. 8 as theType C canister system where there are two PPAV honeycomb partsin-series on the vent-side (volumes 502 and 504 containing comparativeExamples 21a and 21b). In these tests, the canister system was testedas-received, and then retested with the volumes 502 and 504 exchangedwith inventive example PPAV honeycombs (Examples 20a and 20b) ofequivalent external dimensions and adsorptive properties (BWC and IAC)as each of the two original as-received parts. As shown in FIGS. 34 and35 and Table 13, the results were dramatic for this canister system. Forexample, there were only small differences between the as-receivedcomparative example emissions at higher purge levels of 186-211L and71-81BV, with the few mg lower emissions by the inventive Example 20a+bCbeing 44-47% of the comparative Example 21a+bC results. However, thedifferences were progressively larger at lower purge, to as low as 19%of the comparative results at 52 BV purge, with about 18 mg of emissionsfor inventive Example 20a+bC vs. 97 mg for comparative Example 21a+bC.That low level of emissions is significant, as the BETP emissions targetfor LEV III is <20 mg for the canister system and prior art has notedthe extreme difficulties in meeting LEV III evaporative emissionstargets when less than only 50-80 BV of purge, and especially towards<50 BV purge, is available (see US 2011/0168025 A1, U.S. Pat. No.9,657,691, JSAE 20077051/SAE 2007-01-1929, and Tank tech 2015, Trendsfor Fuel Subsystems (Part 1), “Low Bleed Solutions Meeting LEV III/Tier3 Evaporative Emission Standards”), which are incorporated herein byreference in their entirety). In those cases of extremely low purge, thecommon wisdom has been that it would be necessary to resort to moreextreme means for meeting emissions, including the addition of a heatingor heat exchanger function to the canister system, or even employing asealed fuel tank system to prevent diurnal losses. However, it isapparent from these test data that the use of PPAV adsorbent volumeswith low cell pitch and small channel widths as described hereinsurprisingly and unexpectedly can meet low emissions targets without theneed of heaters or sealed tanks.

TABLE 13 Effect of Purge - LEV III System - CR-V. Example: 21a + bC20a + bC Comparative (C)/Inventive (I): Comparative Inventive CanisterSystem Type: C C Day 2 Day 2 Purge, Liters BV Emissions, mg BVEmissions, mg 210.8 80.4 9.4 80.8 4.4 186.0 71.0 9.4 71.3 4.1 161.2 61.520.4 61.8 6.3 136.4 52.1 97.2 52.3 18.5 124.0 47.3 129.2 47.5 35.1

While it was taught in the art that a higher cell density (higher numbercells per unit of cross-sectional area, or lower distances of cellpitch) of a PPAV monolith will lead to a sharpened mass transfer zone(MTZ) and to a more efficiently saturating adsorbent volume underdynamic flow adsorption, there was observed a surprising lack of anysuch MTZ or efficiency advantage for the tested cell densities, or cellpitch when applying published methods for measuring mass transfer zones,for either saturation of virgin parts or saturation of parts after anadsorption-purge pretreatment protocol. Surprisingly, it was observedthat the described range of cell densities and cell pitch provided abenefit to DBL emissions for inventive examples, including a lack of anysuch MTZ or efficiency effect for the PPAV tested with cell densities,or cell pitches, outside and into the inventive range described herein.

As shown by Rezaei and Webley (2009) for carbon dioxide adsorption withvirgin monolith parts, the expected effect is a symmetrical pivotedsharpening of the breakthrough curve of the adsorbate with increasedcell density, with less mass of adsorbate in the effluent stream beforesaturation. However, for n-butane adsorption, the cell density effectappears to vanish at about 200 cpsi. Valdes-Solis, et al. (2004) showedsimilar widths of the 5%-95% breakthrough profiles in comparing 200 and400 cpsi cell densities for equivalent 150 mm total lengths of sectionedmonoliths. Dynamic adsorption tests with comparative Examples 1 and15-17 and inventive Examples 2-4 and 7 in a virgin state display asharpening of the MTZ breakthrough as cell density was increased from 30cpsi, a hydraulic diameter-based cell pitch of about 4 mm, (Example 15),however, the MTZ sharpening progressively diminished with increased celldensity and decreased cell pitch. A significant aspect of these examplesfrom this comparison is that the examples are of about the same externaldimensions, BWC, and carbon ingredient properties and differ only thecell structure, i.e., channel size and pitch. The dynamic adsorptionefficiency to 95% saturation (DAE_(V95%)) was about 50% for Example 15,and then reached an efficiency plateau of about 60-70% by a cell densityof about 200 cpsi (FIG. 36 ), and a cell pitch of about 2 mm (FIG. 37 ).Therefore, any benefit of the examples in canister system emissionsperformance by the inventive examples was not predictable from thedynamic adsorption MTZ and efficiency behavior of the virgin parts (SeeTables 14-17).

TABLE 14 Dynamic Adsorption Test—35 × 150 4.1-4.7 BWC. Example 15 16 171 2 3 4 7 Comparative (C)/Inventive (I) C C C C I I I I Caliper length(mm); L 150.2 151.3 150.6 150.2 151.2 150.9 150.5 151.2 Caliper diameter(mm); D_(o,c) 35.0 35.3 35.3 34.7 34.9 34.4 34.8 35.0 Wall thickness(mm) avg; t_(w,avg) 0.848 0.409 0.628 0.309 0.276 0.233 0.267 0.421Hydraulic diameter Cell pitch (mm); CP_(Dh) 4.537 2.201 1.902 1.5921.190 1.118 0.936 0.836 Cell density (cpsi); n_(c)/(πD_(o) ²/4) 30 123168 239 419 465 667 770 BWC, g/dL 4.31 4.29 4.70 4.13 4.54 4.18 4.454.45 IAC, g/L 18.5 18.9 20.3 17.1 19.5 16.7 19.4 17.8 VirginPart—Initial saturation adsorption step: Time at 5% BT (min); t_(V5%)9.0 19.5 25.2 19.7 24.8 23.9 29.7 27.4 Total C4 adsorbed at t_(V5%) (g);m_(ads, V5%) 1.41 3.08 3.98 3.08 3.89 3.76 4.68 4.33 Total effluent C4at t_(V5%) (g); m_(efl, V5%) 0.005 0.010 0.011 0.039 0.033 0.032 0.0330.012 Efficiency at t_(V5%); DAE_(V5%) 99.6% 99.7% 99.7% 98.7% 99.2%99.2% 99.3% 99.7% Bleedthrough contribution between t_(V5%) & t_(V95%)0.003 0.003 0.002 0.002 0.002 0.002 0.001 0.002 (g); m_(efl, VB5-95%)Time for 95% BT beyond initial bleedthrough 71.4 72.5 64.2 61.3 62.662.4 57.4 66.2 (min); t_(V95%) MTZ effluent between t_(V5%) & t_(V95%)(g); 5.52 5.33 3.92 3.89 3.70 4.11 2.99 3.89 m_(efl, VM5-95%) Totaleffluent at t_(V95%) (g); m_(efl, V95%) 5.53 5.34 3.94 3.93 3.73 4.143.03 3.90 Total adsorbed at t_(V95%) (g); m_(ads, V95%) 5.77 6.14 6.225.78 6.19 5.74 6.07 6.58 Total butane delivered at t_(V95%) (g);m_(del, V95%) 11.30 11.49 10.16 9.71 9.92 9.89 9.09 10.48 Efficiency att_(V95%); D_(AEV95%) 51% 53% 61% 60% 62% 58% 67% 63% Cycled Part—Afterinitial saturation adsorption and purge steps: Time for 5% BT beyondbleedthrough (min); t_(C5%) 47 191 145 229 333 267 256 277 Total butaneadsorbed at t_(C5%) (g); m_(ads, C5%) 0.064 0.284 0.215 0.341 0.5140.412 0.390 0.432 Bleedthrough at t_(C5%) (g); m_(efl, C5%) 0.014 0.0350.027 0.041 0.040 0.028 0.037 0.030 Efficiency at t_(C5%); DAE_(C5%) 82%89% 89% 89% 93% 94% 91% 94% Bleedthrough contribution between t_(C5%) &t_(C95%) 0.037 0.037 0.029 0.029 0.015 0.029 0.015 0.028 (g);m_(efl, CB5-95%) MTZ effluent between t_(C5%) & t_(C95%) (g); 0.2850.547 0.322 0.341 0.318 0.415 0.283 0.427 m_(efl, CM5-95%) Totaleffluent at t_(C95%) (g); m_(efl, C95%) 0.337 0.621 0.378 0.411 0.3730.473 0.335 0.484 Time for 95%BT beyond bleedthrough (min); 375 734 553630 676 674 608 666 t_(C95%) Total butane adsorbed at t_(C95%); (g);m_(ads,C95%) 0.289 0.603 0.544 0.639 0.753 0.651 0.679 0.626 Totalbutane delivered at t_(C95%) (g) 0.626 1.223 0.922 1.050 1.126 1.1241.013 1.110 Efficiency at t_(C95%); DAE_(C95%) 46% 49% 59% 61% 67% 58%67% 56% Time for 25% influent in effluent (min); 68 283 282 330 422 337382 336 tc_(0.125 vol %) Bleedthrough contribution between 0.002 0.0070.010 0.007 0.004 0.007 0.005 0.006 t_(C5%) & tc_(0.125) vol % (g);m_(efl, CB5%-0.125 vol) _(%) MTZ effluent between t_(C5%) &t_(C0.125 vol %) (g); 0.006 0.021 0.030 0.023 0.018 0.032 0.025 0.029m_(efl, CM5%-0.125 vol %) Total effluent at t_(C0.125 vol %) (g);m_(efl, C0.125 vol %) 0.022 0.063 0.067 0.071 0.063 0.067 0.067 0.065Total butane adsorbed at t_(C0.125 vol %); (g); 0.092 0.409 0.403 0.4790.641 0.494 0.570 0.495 m_(ads, C0.125 vol %) Total butane delivered att_(C0.125 vol %) (g) 0.11 0.47 0.47 0.55 0.70 0.56 0.64 0.56 Efficiencyat t_(C.0125 vol %); DAEC_(0.125 vol %) 81% 87% 86% 87% 91% 88% 89% 88%

TABLE 15 Dynamic Adsorption Test - High dP Examples. Example 13 14Comparative (C)/Inventive (I) C C Caliper length (mm); L 151.0   152.0  Caliper diameter (mm); D_(o, c) 35.0   35.4   Wall thickness (mm) avg;t_(w, avg) 0.966 0.911 Hydraulic diameter Cell pitch (mm); CP_(Dh) 1.6361.637 Cell density (cpsi); n_(c)/(πD_(o) ²/4) 228     235     BWC, g/dL2.78  4.43  IAC, g/L 12.4   20.4   Virgin Part - Initial saturationadsorption step: Time at 5% BT (min); t_(V5%) 13.8   23.2   Total C4adsorbed at t_(V5%) (g); m_(ads, V5%) 2.16  3.64  Total effluent C4 att_(V5%) (g); m_(efl, V5%) 0.022 0.027 Efficiency at t_(V5%); DAE_(V5%)99.0%  99.3%  Bleedthrough contribution between t_(V5%) & t_(V95%) 0.0010.002 (g); m_(efl, VB5-95%) Time for 95% BT beyond initial bleedthrough36.3   65.1   (min); t_(V95%) MTZ effluent between t_(V5%) & t_(V95%)(g); 1.99  4.01  m_(efl, VM5-95%) Total effluent at t_(V95%) (g);m_(efl, V95%) 2.02  4.04  Total adsorbed at t_(V95%) (g); m_(ads, V95%)3.73  6.27  Total butane delivered at t_(V95%) (g); m_(del, V95%) 5.75 10.30  Efficiency at t_(V95%); DAE_(V95%) 65% 61% Cycled Part - Afterinitial saturation adsorption and purge steps: Time for 5% BT beyondbleedthrough (min); t_(C5%) 123     173     Total butane adsorbed att_(C5%) (g); m_(ads, C5%) 0.183 0.258 Bleedthrough at t_(C5%) (g);m_(efl, C5%) 0.022 0.030 Efficiency at t_(C5%); DAE_(C5%) 89% 89%Bleedthrough contribution between t_(C5%) & t_(C95%) 0.017 0.021 (g);m_(efl, CB5-95%) MTZ effluent between t_(C5%) & t_(C95%) (g); 0.2350.267 m_(efl, CM5-95%) Total effluent at t_(C95%) (g); m_(efl, C95%)0.274 0.318 Time for 95% BT beyond bleedthrough (min); 427     539    t_(C95%) Total butane adsorbed at t_(C95%); (g); m_(ads, C95%) 0.4380.581 Total butane delivered at t_(C95%) (g) 0.712 0.899 Efficiency att_(C95%); DAE_(C95%) 61% 65% Time for 25% influent in effluent (min);t_(C0.125 vol %) 252     322     Bleedthrough contribution between 0.0070.008 t_(C5%) & t_(C0.125 vol %) (g); m_(efl, CB5%-0.125 vol %) MTZeffluent between t_(C5%) & t_(C0.125 vol %) (g); 0.029 0.034m_(efl, CM5%-0.125 vol %) Total effluent at t_(C0.125 vol %) (g);m_(efl, C0.125 vol %) 0.058 0.072 Total butane adsorbed att_(C0.125 vol %); (g); 0.361 0.464 m_(ads, C0.125 vol %) Total butanedelivered at t_(C0.125 vol %) (g) 0.42  0.54  Efficiency att_(C0.0125 vol %); DAE_(C0.125 vol %) 86% 87%

TABLE 16 Dynamic Adsorption Test—Alternative BWC, carbon and dimension.Example 6 5 8 9 10 11 Comparative (C)/Inventive (I) C I C I C I Caliperlength (mm); L 150.0 151.5 142.5 142.6 150.7 150.6 Caliper diameter(mm); D_(o,c) 35.0 35.0 42.2 42.3 36.0 34.4 Wall thickness (mm) avg;t_(w,avg) 0.675 0.293 0.312 0.291 0.348 0.264 Hydraulic diameter Cellpitch (mm); CP_(Dh) 1.995 0.943 1.610 0.963 1.640 0.894 Cell density(cpsi); n_(c)/(πD_(o) ²/4) 150 660 230 669 227 733 BWC, g/dL 5.92 5.472.95 2.98 3.01 2.86 IAC, g/L 26.3 24.6 10.4 10.4 9.9 10.0 VirginPart—Initial saturation adsorption step: Time at 5% BT (min); t_(V5%)37.2 22.9 17.9 20.1 34.3 29.0 Total C4 adsorbed at t_(V5%) (g);m_(ads, V5%) 5.87 3.60 2.81 3.17 5.37 4.54 Total effluent C4 at t_(V5%)(g); m_(efl, V5%) 0.024 0.021 0.017 0.016 0.059 0.043 Efficiency att_(V5%); DAE_(V5%) 99.6% 99.4% 99.4% 99.5% 98.9% 99.1% Bleedthroughcontribution between t_(V5%) & t_(V95%) 0.003 0.003 0.002 0.002 0.0020.001 (g); m_(efl, VB5-95%) Time for 95% BT beyond initial bleedthrough92.2 84.0 57.3 56.2 63.2 52.0 (min); t_(V95%) MTZ effluent betweent_(V5%) & t_(V95%) (g); 6.00 5.17 3.67 3.27 2.49 1.79 m_(efl, VM5-95%)Total effluent at t_(V95%) (g); m_(efl, V95%) 6.03 5.19 3.69 3.29 2.551.83 Total adsorbed at t_(V95%) (g); m_(ads, V95%) 8.57 8.11 5.38 5.607.45 6.41 Total butane delivered at t_(V95%) (g); m_(del, V95%) 14.6013.31 9.07 8.89 10.00 8.24 Efficiency at t_(V95%); D_(AEV95%) 59% 61%59% 63% 74% 78% Cycled Part—After initial saturation adsorption andpurge steps: Time for 5% BT beyond bleedthrough (min); t_(C5%) 137 254363 408 203 333 Total butane adsorbed at t_(C5%) (g); m_(ads, C5%) 0.1970.380 0.561 0.635 0.309 0.501 Bleedthrough at t_(C5%) (g); m_(efl, C5%)0.031 0.043 0.044 0.044 0.030 0.054 Efficiency at t_(C5%); DAE_(C5%) 86%90% 93% 93% 91% 90% Bleedthrough contribution between t_(C5%) & t_(C95%)0.024 0.015 0.014 0.010 0.020 0.024 (g); m_(efl, CB5-95%) MTZ effluentbetween t_(C5%) & t_(C95%) (g); 0.220 0.205 0.308 0.251 0.318 0.410m_(efl, CM5-95%) Total effluent at t_(C95%) (g); m_(efl, C95%) 0.2750.263 0.366 0.306 0.368 0.488 Time for 95%BT beyond bleedthrough (min);419 525 683 649 683 753 t_(C95%) Total butane adsorbed at t_(C95%); (g);m_(ads,C95%) 0.424 0.612 0.773 0.776 0.769 0.767 Total butane deliveredat t_(C95%) (g) 0.699 0.875 1.138 1.082 1.138 1.255 Efficiency att_(C95%); DAE_(C95%) 61% 70% 68% 72% 68% 61% Time for 25% influent ineffluent (min); 213 345 440 449 408 431 tc_(0.125 vol %) Bleedthroughcontribution between 0.007 0.005 0.003 0.002 0.009 0.006 t_(C5%) &tc_(0.125) vol % (g); m_(efl, CB5%-0.125 vol) _(%) MTZ effluent betweent_(C5%) & t_(C0.125 vol %) (g); 0.019 0.020 0.016 0.009 0.042 0.022m_(efl, CM5%-0.125 vol %) Total effluent at t_(C0.125 vol %) (g);m_(efl, C0.125 vol %) 0.057 0.068 0.063 0.055 0.081 0.082 Total butaneadsorbed at t_(C0.125 vol %); (g); 0.298 0.507 0.671 0.694 0.599 0.637m_(ads, C0.125 vol %) Total butane delivered at t_(C0.125 vol %) (g)0.35 0.58 0.73 0.75 0.68 0.72 Efficiency at t_(C.0125 vol %);DAEC_(0.125 vol %) 84% 88% 91% 93% 88% 89%

Potentially more pertinent performance predictor for a PPAV monolithintended for a cycled application such as evaporative emissions control,could be the dynamic adsorption MTZ properties after the PPAV monolithhad been cycled through an adsorption and purge pretreatment, as taughtby US 2020/0018265. In applying this test for the Examples 1-4, 7, and15-17 of about the same external dimensions, BWC, and carbon ingredientproperties, there was a convergence of the breakthrough MTZ as celldensity was increased from its lowest value, e.g., cell pitch wasdecreased from its highest value. For example, there was a significantlyearly breakthrough and early saturation of the lowest cell density PPAV,Example 15, attributed to a lack of effectiveness of the purgepretreatment for rejuvenating its carbon by virtue of its wide channelwidths, and giving a low cycled dynamic adsorption efficiency to 95%saturation (DAE_(C 95%)) of only about 45%. As cell density and cellpitch were increased across the Examples, the DAE_(C95%) increased to aplateau of about 55-65% by a cell density of about 200 cpsi and a cellpitch of about 2 mm (see FIGS. 38 and 39 , respectively), with nodistinguishing dynamic adsorption efficiency behavior by the inventiveexamples. In considering the abbreviated metric of 25% saturation (0.125vol % n-butane effluent for the 0.5 vol % influent) described in US2020/0018265, there was likewise a plateau in dynamic adsorptionDAE_(C 25% sat), according to cell density (FIG. 40 ) and cell pitch(FIG. 41 ), and, again, with no distinguishing dynamic adsorptionefficiency behavior by the inventive examples. As a measure of systemcapacity effects, the canister systems containing either the comparativeor inventive examples showed no difference in GWC which had itsadsorption cycle endpoint triggered by a cumulative breakthrough massemanating from the vent-side PPAV volume (see FIG. 45 ). Therefore, inpractice within a canister system, the effect of the high cell density,low cell pitch pf the PPAV part on the system's vent-side was strictlyon the emissions performance of the system to which it was installed,without any significant benefit, or detriment, to that system's workingcapacity, consistent with the lack of differentiating dynamic adsorptionperformance of the standalone PPAV parts.

TABLE 17 Dynamic Adsorption Test, including slit-shaped cells. Example24 25 22 23 Comparative (C)/Inventive (I) C-slit C-slit C I Caliperlength (mm); L 151.5 151.4 150.5 150.7 Caliper diameter (mm); D_(o,c)29.3 29.4 29.7 28.8 Wall thickness (mm) avg; t_(w,avg) x-axis y-axisx-axis y-axis 0.304 0.264 0.254 0.336 0.306 0.358 Plurality channelwidth (mm) avg; t_(c,avg) 3.893 0.918 2.722 0.922 1.353 0.916 Pluralitywidth cell pitch (mm); CP_(tc) = t_(c,avg) + t_(w,avg) 4.147 1.254 3.0801.228 1.658 1.180 Average channel hydraulic diameter (mm);4ΣA_(c)/ΣP_(c) 1.288 1.218 1.275 0.894 Cell density (cpsi);n_(c)/(πD_(o) ²/4) 151 174 234 441 BWC, g/dL 4.30 4.30 4.04 4.28 IAC,g/L 18.3 17.0 17.3 17.3 Virgin Part-Initial saturation adsorption step:Time at 5% BT (min); t_(V5%) 16.37 17.40 15.74 18.50 Total C4 adsorbedat t_(V5%) (g); m_(ads, V5%) 2.58 2.74 2.48 2.91 Total effluent C4 att_(V5%) (g); m_(efl, V5%) 0.014 0.013 0.014 0.025 Efficiency at t_(V5%);DAE_(V5%) 99.5% 99.5% 99.4% 99.2% Bleedthrough contribution betweent_(V5%) & t_(V95%) (g); 0.002 0.001 0.001 0.001 m_(efl, VB5-95%) Timefor 95% BT beyond initial bleedthrough (min); 46.2 44.5 42.6 45.3t_(V95%) MTZ effluent between t_(V5%) & t_(V95%) (g); m_(efl, VM5-95%)2.88 2.61 2.73 2.98 Total effluent at t_(V95%) (g); m_(efl, V95%) 2.892.63 2.75 3.01 Total adsorbed at t_(V95%) (g); m_(ads, V95%) 4.43 4.423.99 4.17 Total butane delivered at t_(V95%) (g); m_(del, V95%) 7.327.05 6.74 7.18 Efficiency at t_(V95%); DAE_(V95%) 60% 63% 59% 58% CycledPart-After initial saturation adsorption and purge steps: Time for 5%BTbeyond bleedthrough (min); t_(C5%) 312 320 336 329 Total butane adsorbedat t_(C5%) (g); m_(ads, C5%) 0.479 0.493 0.519 0.507 Bleedthrough att_(C5%) (g); m_(efl, C5%) 0.041 0.041 0.042 0.042 Efficiency at t_(C5%);DAE_(C5%) 92% 92% 93% 92% Bleedthrough contribution between t_(C5%) &t_(C95%) (g); 0.010 0.009 0.007 0.008 m_(efl, CB5-95%) MTZ effluentbetween t_(C5%) & t_(C95%) (g); m_(efl, CM5-95%) 0.200 0.175 0.143 0.182Total effluent at t_(C95%) (g); m_(efl, C95%) 0.251 0.225 0.192 0.232Time for 95% BT beyond bleedthrough (min); t_(C95%) 552 542 495 517Total butane adsorbed at t_(C95%); (g); m_(ads, C95%) 0.670 0.677 0.6340.629 Total butane delivered at t_(C95%) (g) 0.921 0.903 0.826 0.861Efficiency at t_(C95%); DAE_(C95%) 73% 75% 77% 73% Time for 25% influentin effluent (min); t_(C0.125 vol %) 387 403 378 373 Bleedthroughcontribution between 0.003 0.004 0.002 0.002 t_(C5%) & t_(C0.125 vol %)(g); m_(efl, CB5%-0.125 vol %) MTZ effluent between t_(C5%) &t_(C0.125 vol %) (g); 0.015 0.016 0.008 0.009 m_(efl, CM5%-0.125 vol %)Total effluent at t_(C0.125 vol %) (g); m_(efl, C0.125 vol %) 0.0590.060 0.052 0.052 Total butane adsorbed at t_(C0.125 vol %); (g); 0.5860.611 0.579 0.570 m_(ads, C0.125 vol %) Total butane delivered att_(C0.125 vol %) (g) 0.65 0.67 0.63 0.62 Efficiency att_(C0.0125 vol %); DAE_(C0.125 vol %) 91% 91% 92% 92%

The bleedthrough emissions component (m_(efl, C5%)) of the cycled PPAVmight alternatively be considered as a potential predictor of thediurnal breathing loss emissions encountered by the canister systemcontaining the PPAV part during the BETP test. However, no suchcorrelation was evident. For example, in comparing comparative Examples1, and 15-17 with inventive Examples 2-4 and 7, there was no distinctivelevel between inventive and comparative examples for the bleedthroughmass before 5% breakthrough, m_(efl, C5%), when considered as a mass(FIG. 42 ), as a percentage of total influent before 95% MTZbreakthrough (FIG. 43 ) or as percentage of total mass loaded before 95%MTZ breakthrough (FIG. 44 ). Therefore, the performance of the PPAV partas an adsorbent volume component within the canister system was notpredictable from available test methods for dynamic adsorption (SeeTables 14-17). Indeed, in special comparative tests where the vaporchallenges imposed on the vent-side PPAV were measured in the breathingloss step of the BETP test, there actually appeared to be an increasedchallenge to the auxiliary canister containing the PPAV for the systemswhere the PPAV part's cell density was increased and cell pitch wasdecreased. In these tests with the Type A canister system, the PPAV partwas removed just prior to the DBL portion of the BETP protocol(auxiliary canister 300 removed in FIG. 5 ) and the DBL emissions weremeasured. As shown in Table 18, vapor load imposed by the main canisterduring day 2 of the DBL portion of the BETP protocol (in repeatexperiments with each example, but with the DBL emissions step of theBETP protocol conducted with the auxiliary canister 300 removed)surprisingly increased about linearly with the cell density of the PPAVpart that had been installed within the auxiliary canister during theprior preparation steps, meaning that systems with the inventiveexamples in place provided the system with low emissions performancedespite the additional vapor load challenge.

TABLE 18 Examples with PPAV removed. Comparative Inventive InventiveExample 1 Example 2 Example 4 Canister System GWC, g 143.8 143.2 143.0PPAV BWC, g/dL 4.13 4.54 4.45 Average channel hydraulic diameter (mm);t_(c, Dh) = 1.28 0.91 0.67 4ΣA_(c)/ΣP_(c) Hydraulic diameter cell pitch(mm); CP_(Dh) = t_(c, Dh) + 1.59 1.19 0.94 t_(w, avg) Cell Density(cpsi); n_(c)/(πD_(o) ²/4) 239 419 667 Day 2 Emissions, mg 46.0 29.223.1 Emissions with Auxiliary Canister 300 Removed Comparative InventiveInventive Example 1R Example 2R Example 4R Day 2 Emissions, mg 830 858932

While not being bound by theory, it appears that one central factor isthe bulk phase mass transfer within the PPAV monolith channels, withnarrow channel dimensions being favorable, as afforded by a high celldensity. However, it does not appear that a narrow channel width issufficient for the low emissions effect (see Examples 14, 24 and 25. Asecond factor appears to additionally be sufficient total open area asalso afforded by a high cell density, such that the velocity of gas flowthrough the PPAV part at some point in the cycling process is notexcessive and so that there is sufficient residence time (See Example 14with relatively narrow channel width, but also with insufficient openarea from a conventional cell density and pitch). Nonetheless, it isclear from the inventive examples that follow the embodiments teach amethod for attaining unexpectedly low bleed emissions with a evaporativeemissions canister system, even when the amount of purge is exceedinglysmall. Furthermore, the surprising effect on DBL emissions for thecanister system is not predicted by available tests of properties anddynamic performance of the PPAV part alone.

The contents of all references, patents, pending patent applications andpublished patents, cited throughout this application are herebyexpressly incorporated by reference.

Those skilled in the art will recognize or be able to ascertain using nomore than routine experimentation, many equivalents to the specificembodiments of the invention described herein. Such equivalents areintended to be encompassed by the following claims. It is understoodthat the detailed examples and embodiments described herein are given byway of example for illustrative purposes only, and are in no wayconsidered to be limiting to the invention. Various modifications orchanges in light thereof will be suggested to persons skilled in the artand are included within the spirit and purview of this application andare considered within the scope of the appended claims. For example, therelative quantities of the ingredients may be varied to optimize thedesired effects, additional ingredients may be added, and/or similaringredients may be substituted for one or more of the ingredientsdescribed. Additional advantageous features and functionalitiesassociated with the systems, methods, and processes of the presentinvention will be apparent from the appended claims. Moreover, thoseskilled in the art will recognize, or be able to ascertain using no morethan routine experimentation, many equivalents to the specificembodiments of the invention described herein. Such equivalents areintended to be encompassed by the following claims.

We claim:
 1. An evaporative emission control canister system comprising:one or more canisters including a fuel-side adsorbent volume, and atleast one vent-side parallel passage adsorbent volume (PPAV), whereinthe at least one vent-side PPAV comprises an outer surface and aplurality of parallel passages or channels extending therethroughparallel to the outer surface, and wherein the parallel passages orchannels are configured to have at least one of an average channelhydraulic diameter (t_(c,Dh)) of less than or equal to 1.25 mm, ahydraulic diameter cell pitch (CP_(Dh)) of less than or equal to 1.5 mmor a combination thereof.
 2. The evaporative emission control canistersystem of claim 1, wherein the average channel hydraulic diameter(t_(c, Dh)) is less than or equal to 1.20.
 3. The evaporative emissioncontrol canister system of claim 1, wherein the hydraulic diameter cellpitch (CP_(Dh)) is less than or equal to 1.45 mm.
 4. The evaporativeemission control canister system of claim 1, wherein the PPAV furthercomprises at least one of the following: (i) a plurality channel width(t_(c, avg)) of less than about 1.25 mm; (ii) a plurality channel widthcell pitch (CP_(tc, avg)) of less than about 1.5 mm; (iii) a celldensity of from about 285 to about 1000 cpsi; (iv) a cell wall thicknessof less than about 0.5 mm; (v) a BWC of less than about 10 g/dL; (vi) anincremental adsorption capacity between 5% and 50% n-butane at 25 C ofless than about 50 g/L; or (vii) a combination thereof.
 5. Theevaporative emission control canister system of claim 4, wherein theplurality channel width (t_(c, avg)) of the PPAV is less than about 1.20mm.
 6. The evaporative emission control canister system of claim 4,wherein the plurality channel width cell pitch (CP_(tc, avg)) of thePPAV is less than about 1.45 mm.
 7. The evaporative emission controlcanister system of claim 4, wherein the cell density is from about 300to about 900 cpsi (e.g., from about 400 to about 900 or from about 400to 800 or from about 400 to about 600).
 8. The evaporative emissioncontrol canister system of claim 4, wherein the cell wall thickness ofthe PPAV is from about 0.1 mm to about 0.5 mm.
 9. The evaporativeemission control canister system of claim 4, wherein the at least onevent-side PPAV has a BWC of less than about 9.5 g/dL.
 10. Theevaporative emission control canister system of claim 4, wherein the atleast one vent-side PPAV has a gram-total BWC of less than 10 g.
 11. Theevaporative emission control canister system of claim 4, wherein the atleast one vent-side PPAV has an incremental adsorption capacity (IAC)between 5% and 50% n-butane at 25° C. of less than 45 g/L.
 12. Theevaporative emission control canister system of claim 1, wherein the atleast one vent-side PPAV is a honeycomb or cylindrical honeycombstructure.
 13. The evaporative emission control canister system of claim1, wherein the at least one vent-side PPAV comprises an adsorbentmaterial derived from at least one of wood, wood dust, wood flour,cotton linters, peat, coal, coconut, lignite, carbohydrates, petroleumpitch, petroleum coke, coal tar pitch, fruit pits, fruit stones, nutshells, nut pits, sawdust, palm, vegetables, synthetic polymer, naturalpolymer, lignocellulosic material, or a combination thereof.
 14. Theevaporative emission control canister system of claim 13, wherein the atleast one vent-side PPAV comprises activated carbon or carbon charcoal.15. The evaporative emission control canister system of claim 1, whereinthe system has a two-day diurnal breathing loss (DBL) of no more than 50mg at no more than 315 liters of purge or no more than 150 bed volumes(BV) of purge applied after a 40 g/hr butane loading step as determinedby the 2012 California Bleed Emissions Test Procedure (BETP).
 16. Anevaporative emission control system comprising a fuel tank for storingfuel; an engine having an air induction system and adapted to consumefuel; and one or more canisters including a fuel-side adsorbent volumeand at least one vent-side parallel passage adsorbent volume (PPAV),wherein the at least one vent-side PPAV comprises an outer surface and aplurality of parallel passages or channels extending therethroughparallel to the outer surface, and wherein the parallel passages orchannels are configured to have at least one of an average channelhydraulic diameter (t_(c, Dh)) of less than or equal to 1.25 mm, ahydraulic diameter cell pitch (CP_(Dh)) of less than or equal to 1.5 mmor a combination thereof, wherein the canister includes a fuel vaporinlet conduit connecting the evaporative emission control canistersystem to the fuel tank; a fuel vapor purge outlet conduit connectingthe evaporative emission control canister system to the air inductionsystem of the engine; and a vent conduit for venting the evaporativeemission control canister system to the atmosphere and for admission ofpurge air to the evaporative emission control canister system, whereinthe evaporative emission control canister system is defined by a fuelvapor flow path from the fuel vapor inlet conduit to the fuel-sideadsorbent volume toward the at least one PPAV and the vent conduit, andby an air flow path from the vent conduit to the at least one PPAVtoward the fuel-side adsorbent volume and the fuel vapor purge outlet.17. The evaporative emission control canister system of claim 16,wherein the average channel hydraulic diameter (t_(c, Dh)) is less thanor equal to 1.20 mm.
 18. The evaporative emission control canistersystem of claim 16, wherein the hydraulic diameter cell pitch (CP_(Dh))less than or equal to 1.45 mm.
 19. The evaporative emission controlcanister system of claim 16, wherein the PPAV further comprises at leastone of the following: (i) a plurality channel width (t_(c, avg)) of lessthan about 1.25 mm; (ii) a plurality channel width cell pitch(CP_(tc, avg)) of less than about 1.5 mm; (iii) a cell density of fromabout 285 to about 1000 cpsi; (iv) a cell wall thickness of less thanabout 0.5 mm; (v) a BWC of less than about 10 g/dL; (vi) an incrementaladsorption capacity between 5% and 50% n-butane at 25 C of less thanabout 50 g/L; or (vii) a combination thereof.
 20. The evaporativeemission control canister system of claim 19, wherein the pluralitychannel width (t_(c, avg)) of the PPAV is less than about 1.20 mm (e.g.,less than or equal to 1.10 mm, less than or equal to 1.0 mm).